Color developing agent, azo dye, silver halide photographic light-sensitive material, and image-forming method

ABSTRACT

A color-developing agent of the formula (1-1): 
                 
         wherein X represents a hydrogen atom or a substituent, and   Z represents a carbamoyl, acyl, alkoxycarbonyl, or aryloxycarbonyl group. An azo dye of the formula (2-1): 
                 
           wherein R 1  represents a hydrogen atom or a substituent, and A represents a group of atoms necessary to form the azo dye by the compound of formula (2-1). A silver halide photographic light-sensitive material containing any of the color-developing agent and the azo dye in at least one photographic constitutional layer.

This application is a divisional of application Ser. No. 09/911,727,filed on Jul. 25, 2001, now U.S. Pat. No. 6,555,691, the entire contentsof which are hereby incorporated by reference and for which priority isclaimed under 35 U.S.C. §120; and this application claims priority ofApplication Nos. 2000-224547, 2000-224563 and 2001-040774 filed in Japanon Jul. 25, 2000, Jul. 25, 2000 and Feb. 16, 2001, respectively, under35 USC §119.

FIELD OF THE INVENTION

The present invention relates to a novel color-developing agent, and asilver halide photographic light-sensitive material and image-formingmethod using the color-developing agent. More specifically, the presentinvention relates to a silver halide photographic light-sensitivematerial and image-forming method good in color-forming property at thetime of development.

Further, the present invention relates to a novel 1,2,4-oxadiazolyl azodye, which exhibits excellent absorption characteristics, and which ishigh in fastness to light, heat, humidity, air, chemicals and the like.

Further, the present invention relates to a silver halide colorlight-sensitive material containing an image-forming compound containingthe novel 1,2,4-oxadiazolyl azo dye or a precursor thereof.

BACKGROUND OF THE INVENTION

In a color photographic light-sensitive material, when thelight-sensitive material is exposed to light and thereafter subjected tocolor-development, the resultant oxidized color-developing agent reactswith a coupler, to form a dye image.

The color-development is attained, for example, by dipping an exposedlight-sensitive material in an aqueous alkaline solution (a developingsolution) in which a color-developing agent is dissolved. However, thistechnique have many problems, for example, a problem that the developingsolution tends to be deteriorated with the lapse of time and problemsconcerning treatments of developing solution wastes.

As one measure to solve above problems, a method wherein an aromaticprimary amine developing agent or its precursor is built in thehydrophilic colloid layer of a light-sensitive material is proposed.Further, a method wherein a sulfonylhydrazine-type developing agent isbuilt in the hydrophilic colloid layer of a light-sensitive material isproposed. Examples of these include methods described, for example, inU.S. Pat. No. 803 783, JP-B-58-14671 (“JP-B” means examined Japanesepatent publication), European Patent Nos. 545 491(A1) and 565 165(A1).

However, even these methods cannot attain satisfactory color formationwhen color-developed; and there is the problem of storage stability ofthe light-sensitive material.

In the fields of silver halide photographic light-sensitive materials, aso-called color diffusion transfer method in which a diffusible dye isformed imagewise on a light-sensitive material and the image istransferred and fixed to an image-receiving material, to form a colorimage, is a known technique, and many proposals concerned this have beenmade. In these methods, a compound (a preformed dye) obtained by causingan image-forming dye, which is beforehand colored to havenondiffusibility (the compound will be referred to as a coloranthereinafter), is generally used. Therefore, when the colorant is addedto the same layer containing a silver halide emulsion, an undesired dropin the sensitivity to exposure is caused, because of a filter effect ofthe dye moiety. In order to improve these drawbacks, a so-calledcoupling system is proposed in U.S. Pat. No. 4469773 and JP-B-63-36487in which system a dye is formed by a coupling reaction between anoxidized product of a developing agent, which is produced as a functionof the developing of silver halide, and a coupler. However, thecolor-developing agent described therein has a difficulty in thecompatibility of the storage stability and the activity of the couplingreaction and a difficulty in modifying both the color-developing agentand the coupler to those having resistance to diffusion.

Novel color-developing agents are proposed in JP-A-09-152702 (“JP-A”means unexamined published Japanese patent application) andJP-A-09-152705. In these methods, however, sufficient color-formingproperty is not obtained yet. Also, whether or not there are problemsconcerning the hue and color image stability of a dye to be formed.

Hitherto, color diffusion transfer photography, using an azo dyeimage-forming compound that can supply an azo dye having a diffusibilitydifferent from the image-forming compound itself, as a result ofdevelopment under a basic condition, has been widely known. For example,image-forming compounds that release a yellow dye are described inJP-A-52-7727 and JP-A-54-79031, and U.S. Pat. No. 4,473,672. Also,image-forming compounds that release a magenta dye are described, forexample, in JP-A-49-114424, JP-A-4-331954, and U.S. Pat. No. 3,932,380

However, these yellow and magenta dye image-forming compounds haveinsufficient spectral characteristics of the resultant dye resulting inproblems in color reproducibility, or they have low fastness to light,heat, air, chemicals, and the like. Thus, yellow or magenta dyeimage-forming compounds satisfying all performance requirements have notyet been found, and further improvement has been desired.

SUMMARY OF THE INVENTION

The present invention is a color-developing agent represented by thefollowing formula (1-1):

-   -   wherein X represents a hydrogen atom or a substituent, and Z        represents a carbamoyl, acyl, alkoxycarbonyl, or aryloxycarbonyl        group.

Further the present invention is a silver halide photographiclight-sensitive material, which contains at least one color-developingagent represented by the formula (1-1) on a support.

Further, the present invention is an image-forming method, whichcomprises the step of subjecting the silver halide photographiclight-sensitive material to heat-development.

Further, the present invention is an image-forming method, whichcomprises the step of subjecting the silver halide photographiclight-sensitive material to development, under generation of an alkaliby a slightly soluble metal salt and a complexing agent of the metalsalt.

Further, the present invention is an image-forming method, whichcomprises the step of subjecting the silver halide photographiclight-sensitive material to development by developing an alkalineprocessing solution.

Further, the present invention is an azo dye represented by thefollowing formula (2-1):

wherein R¹ represents a hydrogen atom or a substituent, and A representsa group of atoms necessary for formation of the azo dye by the compoundof the formula (2-1).

Further, the present invention is a silver halide photographiclight-sensitive material, which contains the azo dye represented by theformula (2-1).

Further, the present invention is a silver halide color photographiclight-sensitive material, which contains at least one dye-formingcompound represented by the following formula (2-5) on a support:(Dye)_(q)-X¹—Y  formula (2-5)

wherein Dye represents an azo dye represented by the formula (2-1) orazo dye precursor thereof, X¹ represents a single bond or a connectinggroup which is cleaved in correspondence to or in inverse correspondenceto development, Y represents a group which has a nature of generating adifference in diffusibility of the dye component in correspondence to orin inverse correspondence to reaction of a light-sensitive silver salthaving a latent image imagewise, Dye is bonded to X¹ at a position orpositions of at least one of R¹ and A in the formula (2-1), q is 1 or 2,and when q is 2, Dye's may be the same or different.

Other and further features and advantages of the invention will appearmore fully from the following description, taken in connection with theaccompanying drawing.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a graph showing absorbances of the exemplified dye (DYE-7)according to the present invention and the dye for comparison (D-1) inN,N-dimethylformamide.

DETAILED DESCRIPTION OF THE INVENTION

According to the present invention there is provided the followingmeans.

-   (1) A color-developing agent, represented by the following formula    (1-1):    -   wherein X represents a hydrogen atom or a substituent, and Z        represents a carbamoyl, acyl, alkoxycarbonyl, or aryloxycarbonyl        group.-   (2) The color-developing agent according to item (1), wherein X in    the formula (1-1) is a substituent having at least one selected from    the group consisting of —COOH, —NHSO₂R, —SO₂NHR, —SO₂NHCOR,    —CONHSO₂R, —NHCONHSO₂R, —SO₂NHCONRR, —OH and —SH, in which R    represents an alkyl, aryl or aromatic heterocyclic group which may    be substituted, and R's may be the same or different from each other    and may bond together to form a ring.-   (3) The color-developing agent according to item (1), wherein Z in    the formula (1-1) is a carbamoyl group, in which the nitrogen atom    on the carbamoyl group has at least one hydrogen atom.-   (4) A silver halide photographic light-sensitive material,    containing at least one color-developing agent represented by the    formula (1-1) on a support.-   (5) An image-forming method, comprising the step of subjecting the    silver halide photographic light-sensitive material according to    item (4) to heat-development.-   (6) An image-forming method, comprising the step of subjecting the    silver halide photographic light-sensitive material according to    item (4) to development under generation of an alkali by a metal    salt that is hardly soluble in water and a complexing agent for the    metal salt.-   (7) An image-forming method, comprising the step of subjecting the    silver halide photographic light-sensitive material according to    item (4) to development by developing an alkaline processing    solution.

(Hereinafter, the color-developing agents described in the above (1) to(3), the silver halide photographic light-sensitive material describedin the above (4), and the image-forming method described in the above(5) to (7) are collectively referred to as the first embodiment of thepresent invention.)

-   (8) An azo dye, represented by the following formula (2-1):    -   wherein R¹ represents a hydrogen atom or a substituent, and A        represents a group of atoms necessary to form the azo dye by the        compound of the formula (2-1).-   (9) The azo dye according to item (8), wherein A in the formula    (2-1) is a group represented by the following formula (2-2):    -   wherein R², R³, R⁴ and R⁵ each represents a hydrogen atom or a        substituent, and R² and R³ and/or R⁴ and R⁵ may bond together to        form a ring, and * represents a position which is bonded to the        azo moiety in the formula (2-1).-   (10) The azo dye according to item (8), wherein A in the formula    (2-1) is a group represented by the following formula (2-3):    -   wherein Cα represents a carbon atom, EWG represents a cyano,        carbamoyl or alkoxycarbonyl group, M represents a group of atoms        necessary to form together with the Cα a 5- or 6-memebered        aromatic heteroring, and * represents a position which is bonded        to the azo moiety in the formula (2-1).-   (11) The azo dye according to item (8), wherein A in the formula    (2-1) is a group represented by the following formula (2-4):    -   wherein R⁶ represents a hydrogen atom or a substituent, Cβ        represents a group of atoms necessary to form together with the        N—C—NH a 5- or 6-memebered aromatic heteroring, and * represents        a position which is bonded to the azo moiety in the formula        (2-1).-   (12) A silver halide photographic light-sensitive material,    containing the azo dye represented by the formula (2-1) in item (8).-   (13) A silver halide color photographic light-sensitive material,    containing at least one dye-forming compound represented by the    following formula (2-5) on a support:    (Dye)_(q)-X¹—Y  formula (2-5)

wherein Dye represents the azo dye represented by the formula (2-1) initem (8) or azo dye precursor thereof, X¹ represents a single bond or aconnecting group which is cleaved in correspondence to or in inversecorrespondence to development, Y represents a group which has a natureof generating a difference in diffusibility of the dye component incorrespondence to or in inverse correspondence to reaction of alight-sensitive silver salt having a latent image imagewise, Dye isbonded to X¹ at a position or positions of at least one of R¹ and A inthe formula (2-1) in item (8), q is 1 or 2, and when q is 2, Dye's maybe the same or different.

(Hereinafter, the azo dyes described in the above (8) to (11), thesilver halide photographic light-sensitive material described in theabove (12), and the silver halide color photographic light-sensitivematerial described in the above (13) are collectively referred to as thesecond embodiment of the present invention.)

Herein, the present invention means to include both the first embodimentand the second embodiment, unless otherwise specified.

In the present invention, the color-developing agent represented by theformula (1-1) is preferable as a raw material to obtain the azo dyerepresented by the formula (2-1).

Further, an example of an azo dye preferable in the present inventioninclude the azo dye represented by the formula (2-1) obtainable bycoupling reaction of an oxidation product of the color-developing agentrepresented by the formula (1-1) with a coupler.

The following will describe the compound represented by the formula(1-1) and used in the present invention in detail.

Examples of the substituent represented by X in the formula (1-1)include halogen atoms, alkyl (including cycloalkyl and bicycloalkyl),alkenyl (including cycloalkenyl and bicycloalkenyl), alkynyl, aryl,heterocyclic, cyano, hydroxyl, nitro, carboxyl, alkoxy, aryloxy,silyloxy, heterocylic oxy, acyloxy, carbamoyloxy, alkoxycarbonyloxy,aryloxycarbonyloxy, amino (including anilino), acylamino,aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino,sulfamonylamino, alkyl- and aryl-sulfonylamino, mercapto, alkylthio,arylthio, heterocyclic thio, sulfamoyl, sulfo, alky- and aryl-sulfinyl,alkyl- and aryl-sulfonyl, acyl, aryloxycarbonyl, alkoxycarbonyl,carbamoyl, arylazo, heterocyclic azo, imido, phosphino, phosphinyl,phosphinyloxy, phosphinylamino, and silyl groups.

More specifically, examples of the substituent represented by X includehalogen atoms (such as fluorine, chlorine, bromine and iodine atoms),noncyclic alkyl (preferably, alkyl having 1-30 carbon atoms, such asmethyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl,2-chloroethyl, 2-cyanoethyl, and 2-ethylhexyl), cycloalklyl (preferably,substituted or unsubstituted cycloalkyl having 3-30 carbon atoms, suchas cyclohexyl, cyclopentyl, and 4-n-dodecylcyclohexyl), bicycloalkylgroups (preferably, substituted or unsubstituted bicycloalkyl having5-30 carbon atoms, that is, monovalent groups obtained by removing onehydrogen atom from bicycloalkane having 5-30 carbon atoms, such asbicyclo[1,2,2]heptane-2-yl, and bicyclo[2,2,2]octane-3-yl), and tircyclostructure and higher structures, which have a larger number of rings. Analkyl group in substituents that will be described below (for example,alkyl in alkylthio) represents an alkyl group within the scope of such aconcept.

Examples of the substituent represented by X further include noncyclicalkenyl (preferably, substituted or unsubstituted alkenyl having 2-30carbon atoms, such as vinyl, allyl, prenyl, geranyl and oleyl),cycloalkenyl (preferably, substituted or unsubstituted cycloalkenylhaving 3-30 carbon atoms, that is, monovalent groups obtained byremoving one hydrogen atom from cycloalkene having 3-30 carbon atoms,such as 2-cyclopentene-1-yl, and 2-cyclohexene-1-yl), bicycloalkenyl(substituted or unsubstituted bicycloalkenyl, preferably substituted orunsubstituted bicycloalkenyl having 5-30 carbon atoms, that is,monovalent groups obtained by removing one hydrogen atom frombicycloalkene having one double bond, such asbicyclo[2,2,1]hept-2-ene-1-yl, and bicyclo[2,2,2]oct-2-ene-4-yl),alkynyl (preferably, substituted or unsubstituted alkynyl having 2-30carbon atoms, such as ethynyl, propargyl, and trimethylsilylethynyl),aryl (preferably, substituted or unsubstituted aryl having 6-30 carbonatoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, ando-hexadecanoylaminophenyl), heterocyclic (preferably, monovalent groupsobtained by removing one hydrogen atom from 5- or 6-membered andsubstituted or unsubstituted and aromatic or non-aromatic heterocycliccompounds, and more preferably 5- or 6-membered and aromaticheterocyclic groups having 3-30 carbon atoms, such as 2-furyl,2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano, hydroxyl, nitro,carboxyl, alkoxy (preferably, substituted or unsubstituted alkoxy having1-30 carbon atoms, such as methoxy, ethoxy, isopropoxy, t-butoxy,n-octyloxy, 2-methoxyethoxy), aryloxy (preferably, substituted orunsubstituted aryloxy having 6-30 carbon atoms, such as phenoxy,2-ethylphenoxy, 4-t-butylphenoxy, and 3-nitrophenoxy,2-tetradecanoylaminophenoxy), silyloxy (preferably, silyloxy having 3-20carbon atoms, such as trimethylsilyloxy, and t-butyldimethylsilyloxy),heterocyclic oxy (preferably, substituted or unsubstituted heterocyclicoxy having 2-30 carbon atoms, such as 1-phenyltetrazole-5-oxy, and2-tetrahydropyranyloxy), acyloxy (preferably, formyloxy, substituted orunsubstituted alkylcarbonyloxy having 2-30 carbon atoms, and substitutedor unsubstituted arylcarbonyloxy having 6-30 carbon atoms, such asformyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, andp-methoxyphenylcarbonyloxy), carbamoyloxy (preferably, substituted orunsubstituted carbamoyloxy having 1-30 carbon atoms, such asN,N-dimethylcarbamoyloxy, N,N-diethylcarbamoyloxy,morpholinocarbonyloxy, N,N-di-n-octylaminocarbonyloxy,N-n-octylcarbamoyloxy), alkoxycarbonyloxy (preferably, substituted orunsubstituted alkoxycarbonyloxy having 2-30 carbon atoms, such asmethoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, andn-octylcarbonyloxy), aryloxycarbonyloxy (preferably, substituted orunsubstituted aryloxycarbonyloxy having 7-30 carbon atoms, such asphenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, andp-n-hexadecyloxyphenoxycarbonyloxy), amino (preferably, amino,substituted or unsubstituted alkylamino having 1-30 carbon atoms, andsubstituted or unsubstituted anilino having 6-30 carbon atoms, such asamino, methylamino, dimethylamino, anilino, N-methyl-anilino, anddiphenylamino), acylamino (preferably, formylamino, substituted orunsubstituted alkylcarbonylamino having 1-30 carbon atoms, andsubstituted or unsubstituted arylcarbonylamino having 6-30 carbon atoms,such as formylamino, acetylamino, pyvaroylamino, lauroylamino,benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino),aminocarbonylamino (preferably, substituted or unsubstitutedaminocarbonylamino having 1-30 carbon atoms, such as carbamoylamino,N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, andmorpholinocarbonylamino), alkoxycarbonylamino (preferably, substitutedor unsubstituted alkoxycarbonylamino having 2-30 carbon atoms, such asmethoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino,n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino),aryloxycarbonylamino (preferably, substituted or unsubstitutedaryloxycarbonylamino having 7-30 carbon atoms, such asphenoxycarbonylamino, p-chlorophenoxycarbonylamino,m-n-octyloxyphenoxycarbonylamino), sulfamoylamino (preferably,substituted or unsubstituted sulfamoylamino having 0-30 carbon atoms,such as sulfamoylamino, N,N-dimethylaminosulfonylamino, andN-n-octylaminosulfonylamino), alkyl- and aryl-sulfonylamino (preferably,substituted or unsubstituted alkylsulfonylamino having 1-30 carbonatoms, and substituted or unsubstituted arylsulfonylamino having 6-30carbon atoms, such as methylsulfonylamino, butylsulfonylamino,phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, andp-methylphenylsulfonylamino), mercapto, alkylthio (preferably,substituted or unsubstituted alkylthio having 1-30 carbon atoms, such asmethylthio, ethylthio, n-hexadecylthio), arylthio (preferably,substituted or unsubstituted arylthio having 6-30 carbon atoms, such asphenylthio, and p-chlorophenylthio, m-methoxyphenylthio), heterocyclicthio (preferably, substituted or unsubstituted heterocyclic thio having2-30 carbon atoms, such as 2-benzothiazolylthio, and1-phenyltetrazole-5-ylthio), sulfamoyl (preferably, substituted orunsubstituted sulfamoyl having 0-30 carbon atoms, such asN-ethylsulfamoyl, N-(3-dodecyloxypropyl)sulfamoyl,N,N-dimethylsulfamoyl, N-acetylstilfamoyl, N-benzoylsulfamoyl, andN-(N′-phenylcarbamoyl)sulfamoyl), sulfo, alkyl- and aryl-sulfinyl(preferably, substituted or unsubstituted alkylsulfinyl having 1-30carbon atoms, and substituted or unsubstituted arylsulfinyl having 6-30carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, andp-methylphenylsulfinyl), alkyl- and aryl-sulfonyl (preferably,substituted or unsubstituted alkylsulfonyl having 1-30 carbon atoms, andsubstituted or unsubstituted arylsulfonyl having 6-30 carbon atoms, suchas methylsulfonyl, ethylsulfonyl, phenylsulfonyl, andp-methylphenylsulfonyl), acyl (preferably, formyl, substituted orunsubstituted alkylcarbonyl having 2-30 carbon atoms, and substituted orunsubstituted arylcarbonyl having 7-30 carbon atoms, such as acetyl,pivaloyl, 2-chloroacetyl, stearoyl, benzoyl,p-n-octyloxyphenylcarbonyl), aryloxycarbonyl (preferably, substituted orunsubstituted aryloxycarbonyl having 7-30 carbon atoms, such asphenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, andp-t-butylphenoxycarbonyl), alkoxycarbonyl (preferably, substituted orunsubstituted alkoxycarbonyl having 2-30 carbon atoms, such asmethoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, andn-octadecylcarbonyl), carbamoyl (preferably, substituted orunsubstituted carbamoyl having 1-30 carbon atoms, such as carbamoyl,N-methylcarbamoyl, N,N-dimethylcarbamoyl, N,N-di-n-octylcarbamoyl, andN-(methylsulfonyl)carbamoyl), arylazo and heterocyclic azo (preferably,substituted or unsubstituted arylazo having 6-30 carbon atoms, andsubstituted or unsubstituted heterocyclic azo having 3-30 carbon atoms,such as phenylazo, p-chlorophenylazo,5-ethylthio-1,3,4-thiadiazole-2-ylazo), imido (preferably, N-succimido,and N-phthalimido), phosphino (preferably, substituted or unsubstitutedphosphino having 2-30 carbon atoms, such as dimethylphosphino,diphenylphosphino, and methylphenoxyphosphino), phosphinyl (preferably,substituted or unsubstituted phosphinyl having 2-30 carbon atoms, suchas phosphinyl, dioctyloxyphosphinyl, and diethoxyphosphinyl),phosphinyloxy (preferably, substituted or unsubstituted phosphinyloxyhaving 2-30 carbon atoms, such as diphenoxyphospinyloxy,dioctyloxyphosphinyloxy), phosphinylamino (preferably, substituted orunsubstituted phosphinylamino having 2-30 carbon atoms, such asdimethoxyphosphyinylamino, and dimethylaminophosphinylamino), silylgroups(preferably, substituted or unsubstituted silyl having 3-30 carbonatoms, such as trimethylsilyl, t-butyldimethylsilyl, andphenyldimethylsilyl).

Groups having one or more hydrogen atoms, among the above-mentionedfunctional groups, may be removed the hydrogen atom(s) and may befurther substituted with the above-mentioned group(s). Examples of sucha functional group include alkylcarbonylaminosulfonyl,arylcarbonylaminosulfonyl, alkylsulfonylaminocarbonyl, andarylsulfonylaminocarbonyl groups. Specific examples thereof includemethylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl,acetylaminosulfonyl, and benzoylaminosulfonyl.

Among these groups, preferred are halogen atoms, alkyl, aryl, alkylthio,alkylsulfonyl, arylthio, arylsulfonyl, cyano, carbamoyl, and sulfamoylgroups.

Alkyl and aryl groups are more preferred.

X in the formula (1-1) preferably has at least one substituentrepresented by —COOH, —NHSO₂R, —SO₂NHR, —SO₂NHCOR, —CONHSO₂R,—NHCONHSO₂R, —SO₂NHCONRR, —OH and —SH. The substituent represented by Xmay be any one of these substituents themselves.

R represents an alkyl, aryl or aromatic heterocyclic group which may besubstituted, and R's may be the same or be different and may beconnected to each other to form a ring.

Preferred examples of the above-mentioned substituent are —COOH,—NHSO₂R, —CONHSO₂R, and —NHCONHSO₂R. More preferred examples thereof are—NHSO₂R and —NHCONHSO₂R.

Z represents a carbamoyl, acyl, alkoxycarbonyl, or aryloxycarbonylgroup. Examples of these substituents are the same as described about X.Among theses groups, a carbamoyl group is preferred. A carbamoyl groupwherein its nitrogen atom has a hydrogen atom(s) is particularlypreferred.

As the carbamoyl group, carbamoyl having 1-50 carbon atoms is preferred,and carbamoyl having 8-40 carbon atoms is more preferred. Specificexamples thereof include N-hexadecylcarbamoyl, N-octadecylcarbamoyl,N-3-(2,4-tert-pentylphenoxy)propylcarbamoyl,N-(4-dodecyloxyphenyl)carbamoyl,N-(2-chloro-5-dodecyloxycarbonylphenyl)carbamoyl, andN-naphthylcarbamoyl groups.

Examples of the color-developing agent represented by the formula (1-1)will be shown below. However, the scope of the present invention is notlimited to these exemplified examples.

Next, a general method of synthesizing the compound of the presentinvention will be explained.

SYNTHETIC EXAMPLE 1

Synthesis of Exemplified Compound (R-22)

The exemplified compound (R-22) was synthesized in the followingsynthetic rate. Other compounds can be synthesized in the similar manneras above.

Synthesis of a Compound (T-2)

Into 500 ml of acetonitrile was dissolved 152.0 g of a compound (T-1),and then 40.5 g of hydroxylamine hydrochloride was added thereto in fiveseparate operations under cooling with ice. After the addition, 140 mlof triethylamine was dropwise added thereto in the manner that theinternal temperature would be not over 20 C. After the dropwiseaddition, the solution was subjected to further reaction for one hour.The reaction solution was poured into 2000 ml of 0.5 N hydrochloricacid, and then precipitated crystal was collected by filtration, and wasthen washed with 200 ml of water. Thus, 138.7 g of the compound (T-2)was obtained as white crystal.

Synthesis of a Compound (T-3)

Into 350 ml of acetonitrile,and 47.5 ml of triethylamine was dissolved100.0 g of the compound (T-2), and then 28.1 ml of methanesulfonylchloride was dropwise added thereto at room temperature. At this time,the reaction temperature rose from 24° C. to 32° C. After the dropwiseaddition, the reaction system was heated under reflux for 2 hours. Afterthe reaction, the reaction system was cooled to room temperature andprecipitated crystal was filtered. The filtrate was concentrated into anapproximately half volume under reduced pressure. The residue wasdropwise added to 300 ml of tetrahydrofuran dispersion solution (notcompletely homogenous) in which 60.5 g of water-saturated hydrazine wasdispersed, which was separately prepared and vigorously stirred. At thistime, the reaction temperature rose from 23° C. to 35° C. After thereaction, 600 ml of ethyl acetate and 850 ml of water were addedthereto, and then an extraction operation was performed. The organicphase was dried over anhydrous magnesium sulfate and was thenconcentrated under reduced pressure. The residue was subjected to silicagel column chromatography, to obtain 87.2 g of the compound (T-3) as acolorless oily substance from an outflow of ethyl acetate and n-hexane(1/1).

Synthesis of a Compound (T-5)

Into 1000 ml of ethanol was dissolved 196.2 g of a compound (T-4), andthen 83.4 g of powder of hydroxylamine hydrochloride was added theretoat room temperature. Next, the temperature of the reaction system wasraised. While the reaction system was heated under reflux, 246 ml ofsodium methoxide (28% methanol solution) was dropwise added thereto over30 minutes. Thereafter, the reaction system was heated under reflux for3 hours. After the reaction, the reaction solution was added to 2500 mlof ice water. Precipitated crystal was collected by filtration, and wasthen washed with 300 ml of water. The collected crystal was washed with400 ml of cool isopropyl alcohol, to obtain 173.5 g of the compound(T-5) as yellow powder.

Synthesis of a Compound (T-6)

Into 60 ml of N,N-dimethylacetoamide and 8.6 ml of pyridine wasdissolved 22.9 g of the compound (T-5), and then 16.5 g of phenylchloroformate was dropwise added thereto at room temperature over 20minutes. During the dropwise addition, the reaction temperature rosefrom 24° C. to 32° C. After the dropwise addition, the temperature wasraised to 60° C. and the solution was subjected to reaction for 5 hoursat 60° C. After the reaction, the solution was added to a mixed solutionof 500 ml of water and 20 ml of conc. hydrochloric acid. Precipitatedcrystal was collected by filtration, and was then washed with 300 ml ofwater, to obtain 14.7 g of the compound (T-6) as pale yellow crystal.

The resultant crystal was crystal containing one molecule ofN,N-dimethylacetoamide.

Synthesis of a Compound (T-7)

7.7 g of the compound (T-6) was mixed with 45.0 g of phosphorusoxychloride, and the mixture was heated. The compound (T-6) wascompletely dissolved at about 80° C. When the solution was heated to100° C., 2.4 ml of pyridine was dropwise added thereto with sufficientattention. One hour was necessary for the dropwise addition. After thedropwise addition, the solution was subjected to reaction at 110° C. for20 hours. After the reaction, the reaction system was cooled to roomtemperature, and was poured into 300 ml of ice water. Precipitatedcrystal was collected by filtration, and was then washed with 50 ml ofwater. The resultant crystal was suspended into a mixed solution of 50ml of water and 50 ml of acetonitrile, and the suspension was stirredfor 20 minutes. After the stirring, the crystal was collected byfiltration, and was then washed with 20 ml of cool acetonitrile, toobtain 4.7 g of the compound (T-7) as pale red crystal.

Synthesis of an Exemplified Compound (R-22)

Into-50 ml of N,N-dimethylacetoamide was dissolved 4.1 g of the compound(T-3), and then 6.4 g of the compound (T-7) was added thereto in eightseparate operations at room temperature. During the addition, thereaction temperature rose from 24° C. to 28° C. After the addition, thereaction temperature was raised and then the solution was subjected tofurther reaction at 60° C. for 6 hours. After the reaction, 300 ml ofethyl acetate and 350 ml of water were poured thereto to perform anextraction operation. The organic phase was dried over anhydrousmagnesium sulfate, and was-then concentrated under reduced pressure. Theresidue was subjected to silica gel column chromatography, to obtain 5.2g of the exemplified compound (R-22) as colorless amorphous powder froman outflow of ethyl acetate and n-hexane (2/3).

The following will describe the formula (2-1) in detail.

The preferable examples of R¹ include halogen atoms, alkyl (includingcycloalkyl and bicycloalkyl), alkenyl (including cycloalkenyl andbicycloalkenyl), alkynyl, aryl, heterocyclic, cyano, hydroxyl, nitro,carboxyl, alkoxy, aryloxy, silyloxy, heterocylic oxy, acyloxy,carbamoyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, amino (includinganilino), acylamino, aminocarbonylamino, alkoxycarbonylamino,aryloxycarbonylamino, sulfamonylamino, alkyl- and aryl-sulfonylamino,mercapto, alkylthio, arylthio, heterocyclic thio, sulfamoyl, sulfo,alky- and aryl-sulfinyl, alkyl- and aryl-sulfonyl, acyl,aryloxycarbonyl, alkoxycarbonyl, carbamoyl, arylazo, heterocyclic azo,imido, phosphino, phosphinyl, phosphinyloxy, phosphinylamino, and silylgroups.

More specifically, examples of the substituent represented by R¹ includehalogen atoms (such as fluorine, chlorine, bromine and iodine atoms),alkyl (straight-chain, branched or cyclic, and substituted orunsubstituted alkyl, preferably alkyl having 1-10 carbon atoms, such asmethyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, 2-chloroethyl,2-cyanoethyl, and 2-ethylhexyl), and cycloalklyl groups (preferably,substituent or nonsubstituent cycloalkyl having 3-12 carbon atoms, suchas cyclohexyl, cyclopentyl, and 4-n-dodecylcyclohexyl). An alkyl groupin a substituent that will be described below (for example, alkyl inalkylthio) represents the alkyl group within a scope of such a concept.

Examples of the substituent represented by R¹ further include an alkenyl(preferably, substituted or unsubstituted alkenyl having 2-10 carbonatoms, such as vinyl, and allyl), cycloalkenyl (preferably, substitutedor unsubstituted cycloalkenyl having 3-12 carbon atoms, that is,monovalent groups obtained by removing one hydrogen atom fromcycloalkene having 3-12 carbon atoms, such as 2-cyclopentene-1-yl, and2-cyclohexene-1-yl), alkynyl (preferably, substituted or unsubstitutedalkynyl having 2-10 carbon atoms, such as ethynyl, propargyl, andtrimethylsilylethynyl), aryl (preferably, substituted or unsubstitutedaryl having 6-18 carbon atoms, such as phenyl, p-tolyl, naphthyl,m-chlorophenyl, and o-propanoylaminophenyl), heterocyclic (preferably,monovalent groups obtained by removing one hydrogen from 5- or6-membered, substituted or unsubstituted and aromatic or non-aromaticheterocyclic compounds, and more preferably 5- or 6-membered andaromatic heterocyclic groups having 3-18 carbon atoms, such as 2-furyl,2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano, hydroxyl, nitro,carboxyl, alkoxy (preferably, substituted or unsubstituted alkoxy having1-10 carbon atoms, such as methoxy, ethoxy, isopropoxy, t-butoxy,n-octyloxy, 2-methoxyethoxy), aryloxy (preferably, substituted orunsubstituted aryloxy having 6-18 carbon atoms, such as phenoxy,2-methylphenoxy, 4-t-butylphenoxy, and 3-nitrophenoxy,2-butanoylaminophenoxy), silyloxy (preferably, silyloxy having 3-10carbon atoms, such as trimethylsilyloxy, and t-butyldimethylsilyloxy),heterocyclic oxy (preferably, substituted or unsubstituted heterocyclicoxy having 2-18 carbon atoms, such-as 1-phenyltetrazole-5-oxy, and2-tetrahydropyranyloxy), acyloxy (preferably, formyloxy, substituted orunsubstituted alkylcarbonyloxy having 2-10 carbon atoms, and substitutedor unsubstituted arylcarbonyloxy having 6-18 carbon atoms, such asformyloxy, acetyloxy, pivaloyloxy, benzoyloxy,and-p-methoxyphenylcarbonyloxy), carbamoyloxy (preferably, substitutedor unsubstituted carbamoyloxy having 1-12 carbon atoms, such asN,N-dimethylcarbamoyloxy, N,N-diethylcarbamoyloxy,morpholinocarbonyloxy, N-n-octylcarbamoyloxy), alkoxycarbonyloxy(preferably, substituted or unsubstituted alkoxycarbonyloxy having 2-12carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy,t-butoxycarbonyloxy, and n-octylcarbonyloxy), aryloxycarbonyloxy(preferably, substituted or unsubstituted aryloxycarbonyloxy having 7-18carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy,and p-n-propyloxyphenoxycarbonyloxy), amino (preferably, amino,substituted or unsubstituted alkylamino having 1-10 carbon atoms, andsubstituted or unsubstituted anilino having 6-18 carbon atoms, such asamino, methylamino, dimethylamino, anilino, N-methyl-anilino, anddiphenylamino), acylamino (preferably, formylamino, substituted orunsubstituted alkylcarbonylamino having 1-10 carbon atoms, andsubstituted or unsubstituted arylcarbonylamino having 6-18 carbon atoms,such as formylamino, acetylamino, pyvaroylamino, benzoylamino),aminocarbonylamino (preferably, substituted or unsubstitutedaminocarbonylamino having 1-12 carbon atoms, such as carbamoylamino,N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, andmorpholinocarbonylamino), alkoxycarbonylamino (preferably, substitutedor unsubstituted alkoxycarbonylamino having 2-12 carbon atoms, such asmethoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino,n-octyloxycarbonylamino, N-methyl-methoxycarbonylamino),aryloxycarbonylamino (preferably, substituted or unsubstitutedaryloxycarbonylamino having 7-18 carbon atoms, such asphenoxycarbonylamino, p-chlorophenoxycarbonylamino,m-n-octyloxyphenoxycarbonylamino), sulfamoylamino (preferably,substituted or unsubstituted sulfamoylamino having 0-10 carbon atoms,such as sulfamoylamino, N,N-dimethylaminosulfonylamino, andN-n-octylaminosulfonylamino), alkyl- and aryl-sulfonylamino (preferably,substituted or unsubstituted alkylsulfonylamino having 1-10 carbonatoms, and substituted or unsubstituted arylsulfonylamino having 6-18carbon atoms, such as methylsulfonylamino, butylsulfonylamino,phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, andp-methylphenylsulfonylamino), mercapto, alkylthio (preferably,substituted or unsubstituted alkylthio having 1-10 carbon atoms, such asmethylthio, ethylthio, n-hexadecylthio), arylthio (preferably,substituted or unsubstituted arylthio having 6-18 carbon atoms, such asphenylthio, and p-chlorophenylthio, m-methoxyphenylthio), heterocyclicthio (preferably, substituted or unsubstituted heterocyclic thio having2-18 carbon atoms, such as 2-benzothiazolylthio, and1-phenyltetrazole-5-ylthio), sulfamonyl (preferably, substituted orunsubstituted sulfamoyl having 0-10 carbon atoms, such asN-ethylsulfamoyl, N-(3-hydroxypropyl)sulfamoyl, N,N-dimethylsulfamoyl,N-acetylsulfamoyl, N-benzoylsulfamoyl, andN-(N′-phenylcarbamoyl)sulfamoyl), sulfo, alkyl- and aryl-sulfinyl(preferably, substituted or unsubstituted alkylsulfinyl having 1-10carbon atoms, and substituted or unsubstituted arylsulfinyl having 6-18carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, andp-methylphenylsulfinyl), alkyl- and aryl-sulfonyl (preferably,substituted or unsubstituted alkylsulfonyl having 1-10 carbon atoms, andsubstituted or unsubstituted arylsulfonyl having 6-18 carbon atoms, suchas methylsulfonyl, ethylsulfonyl, phenylsulfonyl, andp-methylphenylsulfonyl), acyl (preferably, formyl, substituted orunsubstituted alkylcarbonyl having 2-12 carbon atoms, and substituted orunsubstituted arylcarbonyl having 7-20 carbon atoms, such as acetyl,pivaloyl, 2-chloroacetyl, benzoyl, p-n-propyloxyphenylcarbonyl),aryloxycarbonyl (preferably, substituted or unsubstitutedaryloxycarbonyl having 7-20 carbon atoms, such as phenoxycarbonyl,o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, andp-t-butylphenoxycarbonyl), alkoxycarbonyl (preferably, substituted orunsubstituted alkoxycarbonyl having 2-10 carbon atoms, such asmethoxycarbonyl, ethoxycarbonyl, and t-butoxycarbonyl), carbamoyl(preferably, substituted or unsubstituted carbamoyl having 1-20 carbonatoms, such as carbamoyl, N-methylcarbamoyl, N,N-dimethylcarbamoyl,N,N-di-n-octylcarbamoyl, and N-(methylsulfonyl)carbamoyl), arylazo andheterocyclic azo (preferably, substituted or unsubstituted arylazohaving 6-20 carbon atoms, and substituted or unsubstituted heterocyclicazo having 3-20 carbon atoms, such as phenylazo, p-chlorophenylazo,5-ethylthio-1,3,4-thiadiazole-2-ylazo), imido (preferably, N-succimido,and N-phthalimido), phosphino (preferably, substituted or unsubstitutedphosphino having 2-18 carbon atoms, such as dimethylphosphino,diphenylphosphino, and methylphenoxyphosphino), phosphinyl (preferably,substituted or unsubstituted phosphinyl having 2-18 carbon atoms, suchas phosphinyl, dioctyloxyphosphinyl, and diethoxyphosphinyl),phosphinyloxy (preferably, substituted or unsubstituted phosphinyloxyhaving 2-18 carbon atoms, such as diphenoxyphospinyloxy,dioctyloxyphosphinyloxy), phosphinylamino (preferably, substituted orunsubstituted phosphinylamino having 2-18 carbon atoms, such asdimethoxyphosphyinylamino, and dimethylaminophosphinylamino), silylgroups(preferably, substituted or unsubstituted silyl having 3-12 carbonatoms, such as trimethylsilyl, t-butyldimethylsilyl, andphenyldimethylsilyl).

Groups having one or more hydrogen atoms, among the above-mentionedfunctional groups, may be removed the hydrogen atom(s) and furthersubstituted with the above-mentioned group(s). Examples of such afunctional group include alkylcarbonylaminosulfonyl,arylcarbonylaminosulfonyl, alkylsulfonylaminocarbonyl, andarylsulfonylaminocarbonyl groups. Specific examples thereof includemethylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl,acetylaminosulfonyl, and benzoylaminosulfonyl.

Among the above-mentioned R¹, halogen atoms, alkyl, aryl andheterocyclic groups are-preferred. Aryl and heterocyclic groups are morepreferred. Examples of the substituent thereon are the same as describedabove.

A represents a group of atoms necessary for formation of the azo dye bythe compound of the formula (2-1), and A is preferably a group to give acoupler which has been used in a silver halide photographiclight-sensitive material. The bonding of the coupler to the azo moietyis the same position where the coupler is coupling-reacted with ap-phenylenediamine-series developing agent in a silver halidephotographic light-sensitive material.

The following describe specific examples of the coupler in detail: onpages 291-343 and pages 354-361 in “The Theory of the PhotographicProcess” (4th edition, edited by T. H. James, Macmillian, 1977),JP-A-58-12353, JP-A-58-149046, JP-A-58-149047, JP-A-59-11114,JP-A-59-124399, JP-A-59-174835, JP-A-59-231539, JP-A-59-231540,JP-A-60-2951, JP-A-60-14242, JP-A-60-23474, JP-A-60-66249, on pages80-83 in Research Disclosure No. 37038 (February, 1995), and on pages614-617 in Research Disclosure No. 40145 (September, 1997).

A is particularly preferably a group represented by the followingformula (2-2).

In the formula (2-2), R², R³, R⁴ and R⁵ each represent a hydrogen atomor a substituent. Examples of the substituent are the same as describedabout R¹. Preferred examples of the substituent include halogen atoms,alkyl, cyano, alkoxy, acylamino, aminocarbonylamino,alkoxycarbonylamino, alkyl- and aryl-sulfonylamino, sulfamoyl, sulfo,alkyl- and aryl-sulfinyl, alkyl- and aryl-sulfonyl, acyl,alkoxycarbonyl, and carbamoyl groups. R² and R³ and/or R⁴ and R⁵ maybond together to form a ring. The number of-the atoms in the ring ispreferably 5 to 7. * represents a position which is bonded to the azomoiety in the formula (2-1).

A is preferably a group represented by the following formula (2-3):

In the formula (2-3), Cα represents a carbon atom, EWG represents acyano, carbamoyl or alkoxycarbonyl group, and most preferably a cyanogroup. M represents a group of atoms necessary to form together with theCα a 5- or 6-memebered aromatic heteroring. Examples of the aromaticheteroring include pyrrole, imidazole, pyrazole, 1,2,3-triazole,1,2,4-triazole, tetrazole, 1,3,4-thiadiazole, 1,2,4-thiadiazole,1,3,4-oxadiazole, 1,2,4-oxadiazole, thiazole, oxazole, isothiazole,isooxazole, thiophene, benzoxazole, benzimidazole, benzothiazole,benzoisothiazole, pyrazine, pyrimidine, pyridazine, 1,2,4-triazine,1,3,5-triazine, quinazoline, quinazolone, quinoxaline, synoline,pteridine, and thiazinone rings. To these rings, an aromatic ring suchas a benzene ring or a naphthalene ring, and an aromatic heteroring asmentioned above may be condensed.

Among the exemplified aromatic heterorings, 1,3,4-thiadiazole,1,2,4-thiadiazole, thiazole, benzothiazole, benzoisothiazole andpyrimidine rings are more preferred.

* represents a position which is bonded to the azo moiety in the formula(2-1).

A is preferably a group represented by the following formula (2-4):

wherein R⁶ represents a hydrogen atom or a substituent, and examples ofthe substituent are the same as described about R¹. Preferred examplesof the substituent include alkyl, alkoxy, phenoxy, acylamino,alkoxycarbonyl and carbamoyl groups. Cβ represents a group of atomsnecessary to form together with the N—C—NH a 5- or 6-memebered aromaticheteroring. Preferred examples of the aromatic heteroring includeimidazole, triazole, and benzimidazole rings. * represents a positionwhich is bonded to the azo moiety in the formula (2-1).

In the case that the dye of the present invention is used in a diffusiontransfer image forming method, the dye is used as the followingimage-forming compound (also referred to as dye-providing compound).(Dye)_(q)-X¹—Y  formula (2-5)

In the formula (2-5), Dye represents a dye represented by the formula(2-1) (e.g. yellow azo dye) or a dye precursor (e.g. yellow azo dyeprecursor), X¹ represents a single bond or a connecting group which iscleaved in correspondence to or in inverse correspondence todevelopment, Y represents a group which has a nature of generating adifference in diffusibility of the dye component in correspondence to orin inverse correspondence to reaction of a light-sensitive silver salthaving a latent image imagewise, Dye is bonded to X¹ at a position orpositions of at least one of R¹ and A in the above-mentioned formula(2-1), q is 1 or 2, and when q is 2, Dye's may be the same or different.

The following will describe the compound of the formula (2-5) in detail.

q is 1 or 2, and when q is 2, Dye's may be the same or different.Preferably, q is 1. Dye and X¹ are bonded to each other at a position orpositions of at least one of R¹ and A in the above-mentioned formula(2-1).

Typical examples of the connecting group represented by X¹ includegroups represented by —N(R⁷)— (in which R⁷ is a hydrogen atom or analkyl or substituted alkyl group), —SO₂—, —CO—, alkylene, substitutedalkylene, phenylene, substituted phenylene, naphthylene, substitutednaphthylene, —O—, —SO—, and groups obtained by combining two or more ofthese divalent groups. Preferred are groups represented by —NR⁷—SO₂—,—NR⁷—CO—, and —R⁸—(L)_(k)—(R⁹)_(j)—. R⁸ and R⁹ each represent analkylene, substituted alkylene, phenylene, substituted phenylene,naphthylene, or substituted naphthylene group. L represents —O—, —CO—,—SO—, —SO₂—, —SO₂NH—, —NHSO₂—, —CONH—, or —NHCO—. k is 0 or 1, and j is1 or 0.

Any combination of elements selected from —NR⁷—SO₂—, —NR⁷—CO—, and—R⁸—(L)_(k)—(R⁹)_(j)— is also preferred.

The following will describe Y. Y represents a group which has a naturethat the Y—X¹ bond is cleaved in correspondence to or in inversecorrespondence to a light-sensitive silver halide having a latent image.Such a group is known in the field of photographic chemistry usingdiffusion transfer of a dye, and is described in, for example, U.S. Pat.No. 5,021,334 (corresponding to JP-A-2-184852).

The following will describe Y in detail. (Respective formulae which willbe shown below are described in the state that X¹ is included.)

The bonding form of the Dye moiety and the Y moiety is particularlypreferably a Dye-SO₂NH—Y form.

-   (1) First, Y may be a negative-acting releaser which releases a    photographically useful group in correspondence to development.

As Y classified into the negative-acting releaser, a group of releaserswhich release a photographically useful group from an oxidized productis known. A preferred example of Y of this type is represented by thefollowing formula (Y-1):

In the above-mentioned formula, β represents a group of non-metal atomsnecessary for forming a benzene ring, and a saturated or unsaturatedcarbon ring or heteroring may be condensed to this benzene ring. αrepresents —OZ² or —NHZ³ wherein Z² represents a hydrogen atom or agroup which can generate a hydroxyl group by hydrolysis, and Z³represents a hydrogen atom, an alkyl or aryl group, or a group which cangenerate an amino group by hydrolysis. Z¹ represents an alkyl, aryl,aralkyl, alkoxy, alkylthio, aryloxy, arylthio, acyl, sulfonyl,acylamino, sulfonylamino, carbamoyl, sulfamoyl, ureido, urethane,heterocyclic or cyano group, each of which may have a substituent ifpossible, or a halogen atom, and a is a positive integer. When thenumber of Z¹s is two or more, all of Z¹s may be the same or different.In the formula (Y-1), —X¹ is a group represented by —NHSO₂Z⁴wherein Z⁴is a divalent group.

A more preferred group of the formula (Y-1) is the following formula(Y-2) or (Y-3).

In the above-mentioned formulae, Z²and X¹ have the same meanings asdescribed about the formula (Y-1), and Z⁵ and Z⁶ each represent analkyl, aryl or aralkyl group. These may have a substituent. Z⁵ is morepreferably a secondary or tertiary alkyl group. The total number ofcarbon atoms in Z⁵ and Z⁶ is preferably from 20-50.

Specific examples thereof are described in U.S. Pat. Nos. 4,055,428 and4,336,322, JP-A-51-113624, JP-A-56-16131, JP-A-56-71061, JP-A-56-71060,JP-A-56-710722, JP-A-56-73057, JP-A-57-650, JP-A-57-4043, JP-A-59-60439,JP-B-56-17656 and JP-B-60-25780.

Another example of Y is represented by the following formula (Y-4):

wherein α, X¹, Z¹ and a have the same meanings as described about forthe formula (Y-1), β′ represents a group of non-metal atoms necessaryfor forming a benzene ring, and a saturated or unsaturated carbon ringor heteroring may be condensed to this benzene ring.

Among the groups represented by the formula (Y-4), a group wherein α is—OZ² and β′ forms into a naphthalene skeleton is preferred. Specificexamples thereof are described in U.S. Pat. Nos. 3,928,312 and4,135,929.

Examples of the releaser which releases a photographically useful groupby a reaction similar to the formula (Y-1) or (Y-4) include groupsdescribed in JP-A-51-104343, JP-A-53-46730, JP-A-54-130122,JP-A-57-85055, JP-A-53-3819, JP-A-54-48534, JP-A-49-64436,JP-A-57-20735, JP-B-48-32129, JP-B-48-39165, and U.S. Pat. No.3,443,934.

Examples of a compound which releases a photographically useful groupfrom an oxidized product in accordance with another reaction mechanisminclude hydroquinone derivatives represented by the following formula(Y-5) or (Y-6):

wherein β′ and Z² have the same meanings as described about for theformula (Y-4) and the formula (Y-1), respectively, Z⁷ has the samemeaning as Z², and Z⁸ represents the same substituent as described aboutfor Z¹ or a hydrogen atom. Z² and Z⁷ may be the same or different.Specific examples of this type releaser are described in U.S. Pat. No.3,725,062.

A releaser having a nucleophilic group in its molecule of theabove-mentioned type of hydroquinone derivative releaser may also beused. Specific examples thereof are described in JP-A-4-97347.

Examples of another Y include p-hydroxydiphenylamine derivativesdescribed in U.S. Pat. No. 3,443,939, and hydrazine derivativesdescribed in U.S. Pat. Nos. 3,844,785 and 4,684,604, and on page 22 ofR. D. Vol. 128.

The negative-acting releaser may be represented by the following formula(Y-7):Coup-X¹

wherein Coup is a group which is coupled with an oxidized product of anyone of p-phenylenediamines or p-aminophenols, that is, a group to give acompound which is known as a photographic coupler. Specific examplesthereof are described in G.B. Patent No. 1,330,524.

-   (2) Secondly, Y may be a positive-acting releaser which releases a    photographically useful group in reverse correspondence to    development.

The positive-acting releaser may be a releaser which exhibits a functionwhen the releaser is reduced at the time of development processing.Preferred examples of Y of this type releaser include those representedby the following formula (Y-8):

wherein EAG represents a group which accepts an electron from a reducingsubstance, N represents a nitrogen atom, and W represents an oxygenatom, a sulfur atom or —NZ¹¹—. After EAG receives an electron, the N—Wbond is cleaved. Z¹¹ represents an alkyl or aryl group, and Z⁹ and Z¹⁰each represent a single bonding hand, or a substituent other than ahydrogen atom. Solid lines each represent a bond, and at least one ofdot lines is a bond.

Among the groups represented by the formula (Y-8), preferred is a grouprepresented by the following formula (Y-9):

wherein O represents an oxygen atom (that is, W in the formula (Y-8) isan oxygen atom), and Z¹² represents a group of-atoms having a nature offorming a heteroring containing a N—O bond and causing cleavage of theZ¹²—X¹ bond after the cleavage of the N—O bond. Z¹² may have asubstituent, and a saturated or unsaturated ring may be condensed toZ¹². Z¹³ represents —CO— or —S₂.

Among the groups represented by the formula (Y-9), more preferred is agroup represented by the following formula (Y-10):

wherein Z¹⁴ represents an alkyl, aryl or aralkyl group, Z¹⁵ represents acarbamoyl or sulfamoyl group, Z¹⁶ represents an alkyl, aryl, aralkyl,alkoxy, alkylthio, arylthio, arylthio, cyano or nitro group, or ahalogen atom, b is an integer of 0 to 3, and the substituting positionfor the nitro group in the formula is ortho or para to the nitrogenatom. Z¹⁵ is most preferably a carbamoyl or sulfamoyl group substitutedwith an alkyl group having 12-30 carbon atoms.

Specific examples of this type Y are described in JP-A-62-215270 andU.S. Pat. No. 4,783,396.

Different examples of the positive-acting releaser exhibiting a functionby reduction include BEND compounds described in U.S. Pat. Nos.4,139,379 and 4,139,389, Carquin compounds described in G.B. Patent No.11,445, and releasers described in JP-A-54-126535 and JP-A-57-84453.

When such a releaser to be reduced, the typical example of which isrepresented by the formula (Y-8), is used, a reducing agent is usedtogether with the releaser. LDA compounds which also have, in theirmolecule, a reducing group may be used. Examples thereof are describedin U.S. Pat. No. 4,551,423.

As the positive-acting releaser, there is known a releaser which isincorporated, as a reductant, into a light-sensitive material and isinactivated by oxidization at the time of development processing.Examples of this type releaser include Fields compounds described inJP-A-51-63618 and U.S. Pat. No. 3,980,479, and Hinshaw compoundsdescribed in JP-A-49-111628, JP-A-52-4819, and U.S. Pat. No. 4,199,354.

Examples of this type Y may be represented by the following formula(Y-11):

wherein Z¹⁷ and Z¹⁹ each represent a hydrogen atom or a substituted orunsubstituted acyl, alkoxycarbonyl, or aryloxycarbonyl group, Z¹⁸represents an alkyl, aryl, aralkyl, acyl, alkoxycarbonyl,aryloxycarbonyl, carbamoyl, sulfonyl, or sulfamoyl group, and Z²⁰ andZ²¹, each represent a hydrogen atom, or a substituted or unsubstitutedalkyl, aryl, or aralkyl group. Specific examples thereof are describedin JP-A-62-245270 and JP-A-63-46450.

A positive-acting releaser having another mechanism is a thiazolizinetype releaser. Specific examples thereof are described in U.S. Pat. No.4,468,451 and JP-A-7-159962.

The following will show specific examples of the dye of the formula(2-1) used in the present invention, but the present invention is notlimited to these examples.

First specific examples of A in the formula (2-1) are shown.

In the above formulas, * represents a position which is bonded to thenitrogen atom in the azo moiety. When a hydrogen atom is present at thisposition, the position is bonded to the nitrogen atom in the azo moietyafter the hydrogen atom leaves off.

Next, specific examples of 1,2,4-oxadiazole azo moiety are shown.

In the above formulas, ** represents a position which is bonded to A inthe formula (2-1).

The groups shown above may be arbitrarily combined each other. Thefollowing will show preferred dye examples.

Dye No. C-No P-No DYE-1 C-1 OXA-14 DYE-2 C-2 OXA-3 DYE-3 C-3 OXA-13DYE-4 C-4 OXA-15 DYE-5 C-5 OXA-2 DYE-6 C-6 OXA-2 DYE-7 C-7 OXA-3 DYE-8C-8 OXA-1 DYE-9 C-9 OXA-4 DYE-10 C-10 OXA-5 DYE-11 C-11 OXA-6 DYE-12C-12 OXA-18 DYE-13 C-13 OXA-7 DYE-14 C-14 OXA-8 DYE-15 C-15 OXA-4 DYE-16C-16 OXA-16 DYE-17 C-17 OXA-13 DYE-18 C-18 OXA-12 DYE-19 C-19 OXA-9DYE-20 C-20 OXA-10 DYE-21 C-21 OXA-11 DYE-22 C-22 OXA-13 DYE-23 C-23OXA-14 DYE-24 C-24 OXA-15 DYE-25 C-25 OXA-4 DYE-26 C-26 OXA-5 DYE-27C-27 OXA-6 DYE-28 C-28 OXA-1 DYE-29 C-29 OXA-1 DYE-30 C-30 OXA-1 DYE-31C-31 OXA-2 DYE-32 C-32 OXA-3 DYE-33 C-33 OXA-3 DYE-34 C-34 OXA-11 DYE-35C-35 OXA-13 DYE-36 C-36 OXA-16 DYE-37 C-37 OXA-18 DYE-38 C-38 OXA-14DYE-39 C-39 OXA-1 DYE-40 C-40 OXA-8 DYE-41 C-41 OXA-5 DYE-42 C-42 OXA-6DYE-43 C-43 OXA-1 DYE-44 C-44 OXA-11 DYE-45 C-45 OXA-12 DYE-46 C-46OXA-13 DYE-47 C-47 OXA-14 DYE-48 C-48 OXA-13 DYE-49 C-49 OXA-14 DYE-50C-50 OXA-15 DYE-51 C-51 OXA-16 DYE-52 C-52 OXA-17 DYE-53 C-53 OXA-18DYE-54 C-54 OXA-1 DYE-55 C-55 OXA-9 DYE-56 C-56 OXA-8 DYE-57 C-57 OXA-2DYE-58 C-58 OXA-3 DYE-59 C-59 OXA-14 DYE-60 C-60 OXA-17 DYE-61 C-61OXA-7 DYE-62 C-62 OXA-8 DYE-63 C-63 OXA-11 DYE-64 C-1 OXA-1 DYE-65 C-16OXA-1 DYE-66 C-6 OXA-3 DYE-67 C-9 OXA-3 DYE-68 C-30 OXA-3 DYE-69 C-34OXA-3 DYE-70 C-14 OXA-4 DYE-71 C-60 OXA-4 DYE-72 C-58 OXA-9 DYE-73 C-37OXA-10 DYE-74 C-59 OXA-10 DYE-75 C-13 OXA-14 DYE-76 C-39 OXA-14 DYE-77C-3 OXA-17 DYE-78 C-37 OXA-17 DYE-79 C-34 OXA-3 DYE-80 C-37 OXA-3

The following will show specific examples of the image-forming compoundof the formula (2-5) used in the present invention, but the presentinvention is not limited to these examples.

Compound No. Y

K-1 Y-1 K-2 Y-2 K-3 Y-3

K-4 Y-1 K-5 Y-2 K-6 Y-3

K-7 Y-1 K-8 Y-2 K-9 Y-3

K-10 Y-1 K-11 Y-2 K-12 Y-3

In the above formulas, the group -Y represents a group of the above Y-1,Y-2 or Y-3 bonding at any position after the hydrogen atom on theposition leaves off. Preferably, it is a group of the above Y-1, Y-2 orY-3 bonding at the position shown with *** after the hydrogen atomthereon leaves off.

The dye of the present invention can be synthesized by diazo-couplingreaction of a coupler component with a diazo component.

The following will describe specific synthesis examples of the presentinvention, but the present invention is not limited to these examples.

The exemplified dye (DYE-7) was synthesized in accordance with thefollowing route.

Synthesis of a Compound (B)

Into 1000 ml of ethanol was dissolved 148.12 g of a compound (A), andthen 83.4 g of powder of hydroxylamine hydrochloride was added theretoat room temperature. Then, the temperature of the reaction system wasraised. While the reaction system was heated under reflux, 246 ml ofsodium methoxide (28% methanol solution) was dropwise added thereto over30 minutes. Thereafter, the reaction system was heated and refluxed for3 hours. After the reaction, the reaction solution was added to 2500 mlof ice water. Precipitated crystal was collected by filtration, and wasthen washed with 300 ml of water. The collected crystal was washed with400 ml of cool isopropyl alcohol to obtain 121.5 g of the compound (B)as yellow powder.

Synthesis of a Compound (C)

Into 60 ml of N,N-dimethylacetoamide and 8.6 ml of pyridine wasdissolved 18.1 g of the compound (B), and then 16.5 g of phenylchloroformate was dropwise added thereto at room temperature over 20minutes. During the addition, the reaction temperature rose from 24° C.to 32° C. After the addition, the temperature was raised to 60° C. andthe solution was subjected to reaction for 5 hours. After the reaction,the solution was added to a mixed solution of 500 ml of water and 20 mlof concentrated hydrochloric acid. Precipitated crystal was collected byfiltration, and was then washed with 300 ml of water to obtain 24.9 g ofthe compound (C) as pale yellow crystal.

The resultant crystal was crystal containing one molecule ofN,N-dimethylacetoamide.

Synthesis of a Compound (D)

23.8 g of the compound (C) was mixed with 68.0 g of phosphorusoxychloride, and the mixture was heated. The compound (C) was completelydissolved at about 80° C. When the solution was heated to 100° C., 6.4ml of pyridine was dropwise added thereto with sufficient attention. Onehour was necessary for the addition. After the addition, the solutionwas subjected to reaction at 110° C. for 20 hours. After the reaction,the reaction system was cooled to room temperature, and was poured into700 ml of ice water. Precipitated crystal was collected by filtration,and was then washed with 100 ml of water. The resultant crystal wassuspended into a mixed solution of 50 ml of water and 50 ml ofacetonitrile, and the suspension was stirred for 20 minutes. After thestirring, the crystal was collected by filtration, and was then washedwith 20 ml of cool acetonitrile to obtain 10.4 g of the compound (D) aspale red crystal.

Synthesis of the Compound (E)

Under cooling with water, to a mixed solution of 100 ml oftetrahydrofuran and 6.5 g of water-saturated hydrazine was added 5.1 gof the compound (D) in 5 separate operations. At this time, the reactiontemperature rose from 14° C. to 33° C. After the addition, the solutionwas subjected to further reaction for 30 minutes. After the reaction,the solution was poured into 300 ml of ice water. Precipitated crystalwas collected by filtration, and was then washed with 100 ml of water toobtain 3.5 g of the compound (E) as pale red crystal.

Synthesis of the Compound (F)

Into 50 ml of N,N-dimethylacetoamide was dissolved 3.5 g of the compound(E), and under cooling with ice 3.3 g of tosyl chloride was addedthereto in 7 separate operations. After the addition, the solution wassubjected to further reaction for 2 hours. After the reaction, thesolution was poured into a mixed solution of 200 ml of ice water and 10ml of concentrated hydrochloric acid. Precipitated crystal was collectedby filtration, and was then washed with 100 ml of water. The resultantcrystal was recrystallized from acetonitrile to obtain 2.8 g of thecompound (F) as white crystal.

Synthesis of the Compound (H)

Into 30 ml of ethyl acetate was dissolved 2.8 g of the compound (F), andthereto was added 6.5 g of manganese dioxide. After the addition, thesolution was subjected to further reaction for 1 hour, and then thereaction solution was filtered. To the filtrate were added 50 ml ofwater, 20 ml of ethanol, 4.0 g of potassium carbonate and 2.2 g of thecompound (G), and then the solution was vigorously stirred for 1 hour.After the reaction, the ethyl acetate phase was extracted. The organicphase was dried over anhydrous magnesium sulfate and then ethyl acetatewas distilled off. The residue was subjected to silica gelchromatography to obtain 1.9 g of the compound (H) as red crystal.

Synthesis of the Compound (I)

Into 20 ml of water and 50 ml of ethanol was dissolved 1.5 g of thecompound-(H), and thereto was added 0.9 g of sodium hydrosulfide. Thesolution was heated and refluxed for 1 hour. Thereafter, the solutionwas poured into 100 ml of ice water. Precipitated crystal was collectedby filtration, and was then washed with 30 ml of water to obtain 1.1 gof the compound (I) as red crystal. Synthesis of the exemplified dye(DYE-7)

Into 20 ml of N,N-dimethylacetoamide was dissolved 1.1 g of the compound(I), and thereto was added 0.3 ml of pyridine. Thereto was addeddropwise 0.25 ml of methanesulfonyl chloride at room temperature over 20minutes. During the addition, the reaction temperature rose from 24° C.to 28° C. After the addition, the solution was subjected to furtherreaction for 2 hours. After the reaction, the solution was added to amixed solution of 100 ml of water and 4 ml of concentrated hydrochloricacid- Precipitated crystal was collected by filtration, and was thenwashed with 50 ml of water. The resultant crystal was recrystallizedfrom a mixed solvent of acetonitrile and methanol, to obtain 0.85 g ofthe exemplified dye (DYE-7) as red crystal.

The exemplified dye (DYE-69) was synthesized in accordance with thefollowing route.

Synthesis of the Compound (K)

Into 30 ml of ethyl acetate was dissolved 2.8 g of the compound (F), andthereto was added 6.5 g of manganese dioxide. After the addition, thesolution was subjected to further reaction for 1 hour, and then thereaction solution was filtered. To the filtrate were added 50 ml ofwater, 20 ml of ethanol, 4.0 g of potassium carbonate and 1.4 g of thecompound (J), and then the solution was vigorously stirred for 1 hour.After the reaction, the ethyl acetate phase was extracted. The organicphase was dried over anhydrous magnesium-sulfate and then ethyl acetatewas distilled off. The residue was subjected to silica gelchromatography to obtain 2.2 g of the compound (K) as yellow crystal.

Synthesis of the Compound (L)

Into 20 ml of water and 50 ml of ethanol was dissolved 2.2 g of thecompound (K), and thereto was added 1.6 g of sodium hydrosulfide. Thesolution was heated and refluxed for 1 hour. Thereafter, thesolution-was poured into 100 ml of ice water. Precipitated crystal wascollected by filtration, and was then washed with 30 ml of water toobtain 1.6 g of the compound (L) as yellow crystal.

Synthesis of the Exemplified Dye (DYE-69)

Into 20 ml of N,N-dimethylacetoamide was dissolved 1.6 g of the compound(L), and thereto was added 0.4 ml of pyridine. Thereto was addeddropwise 0.36 ml of methanesulfonyl chloride at room temperature over 20minutes. During the addition, the reaction temperature rose from 24° C.to 27° C. After the addition, the solution was subjected to furtherreaction for 2 hours. After the reaction, the solution was added to amixed solution of 100 ml of water and 4 ml of concentrated hydrochloricacid. Precipitated crystal was collected by filtration, and was thenwashed with 50 ml of water. The resultant crystal was recrystallizedfrom acetonitrile, to obtain 1.1 g of the exemplified dye (DYE-69) asyellow crystal.

The following will describe a method of synthesizing the image-formingcompound used in the-present invention.

The image-forming compound to be used in the present invention caneasily be synthesized with reference to synthesis methods described inthe patent publications referred to to explain the formula (2-5).

Specific synthesis examples according to the present invention will bedescribed hereinafter, but the present invention is not limited to theseexamples.

The exemplified compound (K-1) was synthesized in accordance with thefollowing route.

The compound (M) was synthesized with reference to the synthesis exampleof the above-mentioned dye.

Synthesis of the Exemplified Compound (K-1)

Under the atmosphere of nitrogen, 2.81 g of the compound (Y-1) wasdissolved in 50 ml of N,N-dimethylacetoamide, and then 1.0 ml ofpyridine was added thereto. Then, 6.94 g of the compound (M) was addedthereto under cooling with ice, and then the solution was stirred for 1hour. After the reaction, 500 ml of ethyl acetate and 500 ml of waterwere added thereto, so as to perform extraction. The organic phase wasdried over anhydrous magnesium sulfate, and subsequently ethyl acetatewas distilled off. The residue was subjected to silica gelchromatography, to obtain 6.8 g of the exemplified compound (K-1) as redcrystal.

The color-developing agent of the present invention is used togetherwith a compound (a coupler) that can form a dye by oxidation couplingreaction. This coupler may be a so-called “four-equivalent coupler” or“two-equivalent coupler”, which is used in a conventional system using ap-phenylenediamine-series developing agent. Specific examples of thecoupler are described in detail, for example, in “Theory of ThePhotographic Process” (4th Ed., edited by T. H. James, Macmillan, 1977),pages 291 to 334 and 354 to 361, and in JP-A-58-12353, JP-A-58-149046,JP-A-58-149047, JP-A-59-11114, JP-A-59-124399, JP-A-59-174835,JP-A-59-231539, JP-A-59-231540, JP-A-60-2951, JP-A-60-14242,JP-A-60-23474, and JP-A-60-66249, and in Research Disclosure No. 37038(February, 1995) on pages 80-83, and ibid. No. 40145 (September, 1997)on pages 614-617.

Examples of a coupler that is preferably used in the present inventioninclude exemplified compounds (C-1) to (C-80) described inJP-A-8-286340, and couplers represented by formulae (1) to (12) andpreferably exemplified compounds (C-1) to (C-50) described inJP-A-9-1527-05, but the present invention is not limited to them.

Further, the below-shown couplers (Cp-1) to (Cp-14) can also bementioned as examples of the preferable coupler for use in the presentinvention.

The amount to be added of the coupler that is used with thecolor-developing agent of the present invention, varies according to themolar extinction coefficient (ε) of a produced dye. In order to obtainan image density of 1.0 or more in terms of reflection density, in thecase of a coupler wherein the ε of the dye that will be produced bycoupling is of the order of 5,000 to 500,000, suitably the amount to beadded of the coupler that is used in the present invention, is of theorder of generally 0.01 to 10 mmol/m², and preferably 0.05 to 5 mmol/m²,in terms of the coated amount.

In the case that the color-developing agent of the present invention isincorporated into a light-sensitive material, the developing agent maybe added to any layer thereof (for example, a silver halide emulsionlayer or an intermediate layer). Preferably, the developing agent isincorporated into a silver halide emulsion layer. In the case thatplural silver halide emulsion layers are present, the developing agentis preferably incorporated into all thereof.

The amount of the color-developing agent of the present invention to beadded is generally 0.01 to 100 times, preferably 0.2 to 5 times, theamount of the coupler in molar ratio.

The developing agent may be used by incorporating into a processingsolution instead of a light-sensitive material. In this case, thedeveloping agent is incorporated preferably in an amount of 0.1-100 gand more preferably in an amount of 1-20 g, per liter of the processingsolution.

In the present invention, an auxiliary developing agent can be used.Herein the term “an auxiliary developing agent” means a substance thatfunctions to accelerate the transfer of electrons from thecolor-developing agent to silver halides in the development process ofthe silver halide development; and the auxiliary developing agent is acompound capable of releasing electrons according to the Kendall-Pelzrule.

The auxiliary developing agent in the present invention is preferablyany one of-compounds represented by the formulae (B-1) and (B-2),described in JP-A-08-286340. Examples thereof include ETA-1 to ETA-36described in JP-A-08-2.86340. Compounds represented by the formula (1)described in JP-A-09-146248 are also preferred. Examples thereof includeexemplified compounds D-1 to D-35 described in JP-A-09-146248.

In the present invention, a blocked photographic reagent that willrelease a photographically useful group at the time of processing can beused. Examples of these are described in detail on pages 41 to 42 ofJP-A-09-152704.

The light-sensitive material of the first embodiment of the presentinvention, preferably, has on a base, a photosensitive silver halide, atleast one color-developing agent represented by the above formula (1-1),a coupler, and a binder, and, if required, an organometal salt oxidizingagent, and the like can be contained. In many cases, these componentsare added to the same layer, but they can be separately added todifferent layers if they are in reactive states.

The light-sensitive material, preferably heat-developable colorlight-sensitive material of the second embodiment of the presentinvention basically has on a base, a light-sensitive silver halideemulsion, and a binder, and, if required, an organometal salt oxidizingagent, a dye-providing compound (for example, the compound of formula(2-5); a reducing agent may have this function as described later), orthe like can be contained.

These components are added to the same layer in many cases, but they maybe added to separate layers. For example, when a colored dye-providingcompound is allowed to present in a layer lower than a silver halideemulsion layer, the sensitivity can be prevented from lowering.

Further, a reducing agent is preferably built in the heat-developablelight-sensitive material, but it may be supplied from the outside, forexample, by a method wherein it is diffused from a dye-fixing element asdescribed later.

Hydrophobic additives such as a coupler, a color-developing agent, adye-providing compound, and a nondiffusion reducing agent, which areused in the present invention may be introduced into the layers of thelight-sensitive material (i.e. photographic-constitutional layers suchas hydrophilic colloid layer) by a known method such as a methoddescribed in U.S. Pat. No. 2,322,027. When these compounds are to beintroduced into the layers, a high-boiling point organic solvent asdescribed in U.S. Pat. Nos. 4,555,470, 4,536,466, 4,536,467, 4,587,206,4,555,476, 4,599,296, JP-B-3-62256 may be used, as required, togetherwith a low-boiling point organic solvent having a boiling point as lowas 50° C. to 160° C. Further, these dye-providing compounds such as acoupler and a color-developing agent, nondiffusion reducing agents,high-boiling organic solvents, and the like each can be used singly, orin the form of a combination of two or more. As the case ofcolor-developing agents, the compound represented by formula (1-1) canbe used in combination with another compound that is not included in theformula.

The amount of the high-boiling point organic solvent to be used isgenerally 10 g or less, preferably 5 g or less, and more preferably 1 gto 0.1 g, per g of a dye-providing compound to be used. The amount ofthe solvent is preferably 1 ml or less, more preferably 0.5 ml or lessand particularly preferably 0.3 ml or less, per g of the binder.

A dispersion method that use a polymer, as described in JP-B-51-39853and JP-A-51-59943, and a-method wherein the addition is made with themin the form of a dispersion of fine particles, as described, forexample, in JP-A-62-30242 and-JP-A-63-271339, can also be used.

If the compounds are substantially insoluble in water, besides the abovemethods, a method can be used wherein the compounds may be made intofine particles to be dispersed and contained in a binder.

In dispersing the hydrophobic compound in a hydrophilic colloid, varioussurface-active agents can be used. For example, surface-active agentsdescribed in JP-A-59-157636, pages (37) to (38), and in the RDpublications shown in a table below, can be used.

In the photographic material of the present invention, use can be madeof a compound that can activate the development and make the imagestable. Preferable specific compounds for use are described in U.S. Pat.No. 4,500,626, the 51st column to the 52nd column.

In order to obtain colors ranging widely on the chromaticity diagram byusing three primary colors: yellow, magenta, and cyan, use is made of acombination of at least three silver halide emulsion layersphotosensitive to respectively different spectral regions. For example,a combination of a blue-sensitive layer, a green-sensitive layer, and ared-sensitive layer, and a combination of a green-sensitive layer, ared-sensitive layer, and an infrared-sensitive layer, and a combinationof a red-sensitive layer, an infrared-sensitive layer (1), and aninfrared-sensitive layer (2), as described in JP-A-59-180550,JP-A-64-13546, JP-A-62-253159, and EP-A-479,167, can be mentioned. Eachof the photosensitive layers can be arranged in various orders knowngenerally for color photographic materials. Further, each of thesephotosensitive layers can be divided into two or more layers ifnecessary, as described in JP-A-1-252954. In the heat-developablelight-sensitive material, various non-light-sensitive layers can beprovided, such as a protective layer, an underlayer, an intermediatelayer, a yellow filter layer, and an antihalation layer, between theabove silver halide emulsion layers, or as an uppermost layer or alowermost layer; and on the opposite side of the photographic support,various auxiliary layers can be provided, such as a backing layer.Specifically, for example, layer constitutions as described in theabove-mentioned patent publications, undercoat layers as described inU.S. Pat. No. 5,051,335, intermediate layers containing a solid pigment,as described in JP-A-1-167,838 and JP-A-61-20,943, intermediate layerscontaining a reducing agent or a DIR compound, as described inJP-A-1-129,553, JP-A-5-34,884, and JP-A-2-64,634, intermediate layerscontaining an electron-transfer agent, as described in U.S. Pat. Nos.5,017,454 and 5,139,919, and JP-A-2-235,044, protective layerscontaining a reducing agent, as described in JP-A-4-249,245, orcombinations of these layers, can be provided. It is-preferable todesign a support so that it has antistatic function and the surfaceresistivity of 10¹² Ω·cm or less. Further, in order to improve the colorseparation, various filter dyes can be added.

The silver halide grains used in the present invention are made ofsilver bromide, silver chloride, silver chlorobromide, silverchloroiodide, silver iodobromide, or silver chloroiodobromide. Othersilver salts, such as silver rhodanate, silver sulfide, silver selenide,silver carbonate, silver phosphate, or a silver salt of an organic acid,may be contained in the form of independent grains or as part of silverhalide grains. If it is desired to make the development/desilvering(bleaching, fixing, and bleach-fix) step rapid, silver halide grainshaving a high silver chloride content are desirable. Further, if thedevelopment is to be restrained moderately, it is preferable to containsilver iodide. The preferable silver iodide content varies depending onthe intended photographic material. For example, in the case of X-rayphotographic materials, the preferable silver iodide content is in therange of 0.1 to 15 mol %, and in the case of graphic art and microphotographic materials, the preferable silver iodide content is in therange of 0.1 to 5 mol %. In the case of photographic materials forshooting represented by color negatives, preferably silver halidecontains 1 to 30 mol %, more preferably 5 to 20 mol %, and particularlypreferably 8 to 15 mol %, of silver iodide. It is preferable toincorporate silver chloride in silver iodobromide grains, because thelattice strain can be made less intense.

The silver halide emulsion that is used in the present invention may bea surface-latent-image-type emulsion or an internal-latent-image-typeemulsion. The internal-latent-image-type emulsion is used in combinationwith a nucleator or a light-fogging agent to be used as a directreversal emulsion. When the silver halide grains contained in the silverhalide emulsion for use in the present invention are composed of a mixedcrystal of different silver halides, the grains having uniformcomposition in the individual grain can be used, but it is alsopreferably performed to make the grains have what is called a laminationlayer structure, having multiple layers with different halogencompositions within the individual grain. Examples of the latter includea so-called core-shell emulsion having different compositions in theinner part and surface layer of the grain. Further, in addition to thelamination layer structure as mentioned above, a structure having alocalized phase with a different halogen composition within theindividual grain can also be preferably used. Preferable examples of thegrains having such a structure include grains in which, on the surface,edge, or top of an individual silver halide grain as the mother body, asilver halide with different composition is joined by epitaxial joining.Further, it is also preferable to form the localized phase in the innerparts of the grain. The silver halide grains that constitute the silverhalide emulsion may have a monodisperse or a polydisperse distributionof grain size. A technique is preferably used wherein the gradation isadjusted by mixing monodispersed emulsions having different grain sizeor sensitivity, as described in JP-A-1-167743 or JP-A-4-223463. Thegrain size is preferably 0.1 to 2 μm, and particularly preferably 0.2 to1.5 μm. The crystal habit of the silver halide grains may be any ofregular crystals, such as cubic crystals, octahedral crystals andtetradecahedral crystals; irregular crystals, such-as spherical crystalsand tabular crystals having a high aspect ratio; crystals having crystaldefects, such as twin planes, composite crystals of these, or others.

The grains of the silver halide emulsion for use in the presentinvention preferably have a distribution or a structure with respect tothe halogen composition. Typical examples thereof are grains having adouble structure, or core-shell-type grains wherein the halogencomposition is different in the surface layer and the inside part of thegrains, as disclosed, respectively, in JP-B-43-13162, JP-A-61-215540,JP-A-60-222845, and JP-A-61-75337. Instead of a simple double structure,a triple structure, as described in JP-A-60-222844, an evenlarger-number multilayer structure, or a structure wherein the surfaceof grains having a core-shell double structure has a thin silver halidelayer different in composition from that of the said surface, can beused.

In order to make the inside of grains have a structure, not only theenclosing structure, as mentioned above, but also a so-call junctionedstructure can be used to form grains. Examples thereof are disclosed,for example, in JP-A-59-133540, JP-A-58-108526, European Patent No. 199290(A2), JP-B-58-24772, and JP-A-59-16254. Crystals to be junctionedhave a composition different from that of host crystals, and they can bejunctioned and formed at the edges, corners, or planes of the hostcrystals. Such junctioned crystals can be formed if host crystals have auniform halogen composition or a core-shell-type structure.

In the case of a junctioned structure, not only a combination of silverhalides but also a combination of a silver halide with a silver saltcompound having no rock salt structure, such as silver rhodanate andsilver carbonate, can be used for the junctioned structure. A non-silversalt compound, such as lead oxide, may be used if a junctioned structureis possible.

In the case of grains of silver iodobromide or the like having thesestructures, a preferable mode is that the core part is higher in silveriodide content than the shell part. Reversely, in some cases, grainshaving a lower silver iodide content in the core part than in the shellpart are preferable. Similarly, in the case of grains having ajunctioned structure, the silver iodide content of the host crystals isrelatively higher than that of the junctioned crystals, or this may bereversed. The boundary part of the grains having these structures inwhich different halogen compositions are present, may be distinct orindistinct. Also preferable is a mode wherein the composition iscontinuously changed positively.

It is important that in the case of that two or more silver halides arepresent as mixed crystals, or as silver halide grains having structures,the halogen composition distribution amoung grains is controlled. Themethod of measuring the halogen composition distribution among grains isdescribed in JP-A-60-254032. A desirable property is that the halogendistribution among grains is uniform. In particular, a highly uniformemulsion having a deviation coefficient of 20% or below is preferable.Another preferable mode is an emulsion in which the grain size and thehalogen composition are correlated. An example correlation is a largergrain size with a larger iodine content, and vice versa (smaller grainsize, lower iodine content). Depending on the purpose, the reversedcorrelation or a correlation using some other halogen composition can beused. For this purpose, it is preferable to mix two or more emulsionsdifferent in composition.

It is important to control the silver halide composition near thesurface of grains. An increase in the silver iodide content or thesilver chloride content at the part near the surface changes theadsorption of a dye or the developing speed. Therefore, the silverhalide composition can be chosen in accordance with the purpose. Tochange the halogen composition at the part near the surface, either thestructure enclosing the whole of a grain or the structure wherein onlypart of a grain is attached to another silver halide different inhalogen composition, can be chosen. For example, in the case of atetradecahedral grain having (100) and (111) planes, only one plane ischanged in halogen composition, or in another case, one of the main faceand the side face of a tabular grain is changed in halogen composition.

In the silver halide grains used in the present invention, in accordancewith the purpose, any of regular crystals having no twin plane, andthose described in “Shashin Kogyo no Kiso, Ginen Shashin-hen”, edited byNihon Shashin-gakkai (Corona Co.), page-163, such as single twins havingone twin plane, parallel multiple twins having two or more parallel twinplanes, and nonparallel multiple twins having two or more nonparalleltwin planes, can be chosen and used. An example in which grainsdifferent in shape are mixed is disclosed in U.S. Pat. No. 4,865,964,and if necessary this method can be chosen. In the case of regularcrystals, cubes having (100) planes, octahedrons having (111) planes,and dodecahedral grains having (110) planes, as disclosed inJP-B-55-42737 and JP-A-60-222842, can be used. Further, (h11) planegrains represented by (211), (hh1) plane grains represented by (331),(hk0) plane grains represented by (210) planes, and (hk1) plane grainsrepresented by (321) planes, as reported in “Journal of ImagingScience”, Vol. 30, page 247 (1986), can be chosen and used in accordancewith the purpose, although the preparation is required to be adjusted.Grains having two or more planes-in one grain, such as tetradecahedralgrains having (100) and (111) planes in one grain, grains having (100)and (110) planes in one grain, or grains having (111) and (110) planesin one grain, can be chosen and used in accordance with the purpose.

The value obtained by dividing the diameter of the projected area, whichis assumed to be a circle equivalent in area, by the thickness of thegrain, is called an aspect ratio, which defines the shape of tabulargrains. Tabular grains having an aspect ratio of more than 1 can be usedin the present invention. Tabular grains can be prepared by methodsdescribed, for example, by Cleav in “Photography Theory and Practice”(1930), page 131; by Gutof in “Photographic Science and Engineering”,Vol. 14, pages 248 to 257 (1970); and in U.S. Pat. Nos. 4,434,226,4,414,310, 4,433,048, and 4,439,520, and British Patent No. 2 112 157.When tabular grains are used, such merits are obtained that the coveringpower is increased and the color sensitization efficiency due to asensitizing dye is increased, as described in detail in theabove-mentioned U.S. Pat. No. 4,434,226. The average aspect ratio of 80%or more of all the projected areas of grains is preferably 1 or more butless than 100, more preferably 2 or more but less than 20, andparticularly preferably 3 or more but less than 10. As the shape ofaverage grains, a triangle, a hexagon, a circle, and the like can bechosen. A regular hexagonal shape having six approximately equal sides,described in U.S. Pat. No. 4,798,354, is a preferable mode.

In many cases, the grain size of tabular grains is expressed by thediameter of the projected area assumed to be a circle, and grains havingan average diameter of 0.6 μm or below, as described in U.S. Pat. No.4,748,106, are preferable, because the quality of the image is madehigh. An emulsion having a narrow grain size distribution, as describedin U.S. Pat. No. 4,775,617, is also preferable. It is preferable torestrict the shape of tabular grains so that the thickness of the grainsmay be 0.5 μm or below, and more preferably 0.3 μm or below, because thesharpness is increased. Further, an emulsion in which the grains arehighly uniform in thickness, with the deviation coefficient of grainthickness being 30% or below, is also preferable. Grains in which thethickness of the grains and the plane distance between twin planes aredefined, as described in JP-A-63-163451, are also preferable.

In the case of tabular grain the dislocation lines can be observed by atransmission electron microscope. In accordance with the purpose, it ispreferable to choose grains having no dislocation lines, grains havingseveral dislocation lines, or grains having many dislocation lines.Dislocation introduced straight in a special direction in the crystalorientation of grains, or curved dislocation, can be chosen, and it ispossible to choose from, for example, dislocation introduced throughoutgrains, dislocation introduced in a particular part of grains, anddislocation introduced limitedly to the fringes of grains. In additionto the case of introduction of dislocation lines into tabular grains,also preferable is the case of introduction of dislocation lines intoregular crystalline grains or irregular grains, represented by potatograins. In this case, a preferable mode is that introduction is limitedto a particular part of grains, such as vertexes and edges.

The silver halide emulsion used in the present invention may besubjected to a treatment for making grains round, as disclosed, forexample, in European Patent No. 96 412(B1), or it may be improved in thesurface, as disclosed in West Germany Patent No. 2 306 447(C2) andJP-A-60-221320.

Generally, the grain surface has a flat structure, but it is alsopreferable in some cases to make the grain surface uneven intentionally.Examples are a technique in which part of crystals, for example,vertexes and the centers of planes, are formed with holes, as describedin JP-A-58-106532 and JP-A-60-221320, and ruffled grains, as describedin U.S. Pat. No. 4,643,966.

The grain size of the emulsion used in the present invention isevaluated, for example, by the diameter of the projected area equivalentto a circle using an electron microscope; by the diameter of the grainvolume equivalent to a sphere, calculated from the projected area andthe grain thickness; or by the diameter of a volume equivalent to asphere, using the Coulter Counter method. A selection can be made fromultrafine grains having a sphere-equivalent diameter of 0.05 μm orbelow, and coarse grains having a sphere-equivalent diameter of 10 μm ormore. Preferably, grains of 0.1 μm or more but 3 μm or below are used asphotosensitive silver halide grains.

As the emulsion used in the present invention, an emulsion having a widegrain size distribution, that is, a so-called polydisperse emulsion, oran emulsion having a narrow grain size distribution, that is, aso-called monodisperse emulsion, can be chosen and used in accordancewith the purpose. As the scale for representing the size distribution,the diameter of the projected area of the grain equivalent to a circle,or the deviation coefficient of the sphere-equivalent diameters, isused. If a monodisperse emulsion is used, it is good to use an emulsionhaving such a size distribution that the deviation coefficient ispreferably 25% or below, more preferably 20% or below, and further morepreferably 15% or below.

In some cases, a monodisperse emulsion is defined by the average grainsize distribution based on the weight or number of grains. Further, inorder to allow the photographic material to satisfy the intendedgradation, in an emulsion layer having substantially the same colorsensitivity, two or more monodisperse silver halide emulsions differentin grain size are mixed and applied to the same layer or are applied asoverlaid layers. Further, two or more polydisperse silver halideemulsions can be used as a mixture; or they can be used to form overlaidlayers; or a combination of a monodisperse emulsion and a polydisperseemulsion can be used as a mixture; or the combination can be used toform overlaid layers.

As an emulsion used in the present invention, use can be made of anemulsion containing the above grains. One mode of carrying out thepresent invention is that the color-developing agent of the presentinvention and the emulsion comprising tabular grains whose silverchloride content is 50 mol % or more, are not used in combination.

As the photographic emulsion used in the present invention,specifically, any of silver halide emulsions can be used that areprepared by methods described, for example, in U.S. Pat. No. 4,500,626,column 50; U.S. Pat. No. 4,628,021, Research Disclosure (hereinafterabbreviated to as RD) No. 17,029 (1978), RD No. 17,643 (December 1978),pages 22 to 23; RD No. 18,716 (November 1979), page 648; RD No. 307,105(November 1989), pages 863 to 865; JP-A-62-253159, JP-A-64-13546,JP-A-2-236546, and JP-A-3-110555; and by P. Glafkides in “Chemie etPhisique Photographique” Paul Montel, 1967; by G. F. Duffin in“Photographic Emulsion Chemistry,” Focal Press, 1966; or by V. L.Zelikman et al. in “Making and Coating Photographic Emulsion,” FocalPress, 1964 can be used. That is, any of the acid process, the neutralprocess, the ammonia process, and the like can be used; and to react asoluble silver salt with a soluble halogen salt, any of the single-jetmethod, the double-jet method, a combination thereof, and the like canbe used. In order to obtain a monodisperse emulsion, the double-jetmethod is preferably used. A method wherein grains are formed in thepresence of excess silver ions (the so-called reverse precipitationprocess) can also be used. As one type of the double-jet method, amethod wherein pAg in the liquid phase, in which a silver halide will beformed, is kept constant, that is, the so-called controlled double-jetmethod, can also be used. According to this method, a silver halideemulsion wherein the crystals are regular in shape and whose grain sizeis approximately uniform, can be obtained.

A method in which previously precipitated silver halide grains are addedto a reaction vessel for the preparation of an emulsion, and the methodsdescribed, for example, in U.S. Pat. Nos. 4,334,012, 4,301,241, and4,150,994, are preferable in some cases. These can be used as seedcrystals, or they are effective when they are supplied as a silverhalide for growth. In the latter case, it is preferable to add anemulsion whose grains are small in size, and as an addition method, oneof the following can be chosen: all of the volume is added at onestroke, or the volume is separated and added in portions, or it is addedcontinuously. Further, in some cases, it is also effective to add grainshaving different halogen compositions in order to modify the surface.

It is preferably performed that the light-sensitive silver halideemulsion for use in the present invention is made to contain an ion of atransition metal, such as titanium, iron, cobalt, ruthenium, rhodium,osmium, iridium, and platinum, or an ion of a typical metal, such aszinc, cadmium, thallium, and lead, in the inner part or surface of thegrain, for the various purposes of high sensitivity, contrasting,improving reciprocity law failure, improving latent image stability,improving pressure durability, and the like. These metal ions can beintroduced in the form of salts or complex salts. In particular, whenthe transition metal ion is contained, it is preferable to use it ascomplexes having ammonia, halogens, cyan, thiocyan, nitrosyl, and thelike, as ligands, or complexes having organic ligands, such asimidazole, triazole, pyridine, bipyridine and the like, as ligands.These ligands can be used singly or in combination of multiple kinds ofligands. Moreover, it is also possible to use these compounds singly orin combination of two or more kinds. The amount to be added variesdepending on the purpose of the application; but the amount is generallyon the order of 10⁻⁹ to 10⁻³ mol per mol of the silver halide. When theyare incorporated, they may be incorporated uniformly in the grains, orthey may be localized in the grains or on the surface of the grains.Specifically, emulsions described, for example, in JP-A-2-236542,JP-A-1-116637, and JP-A-5-181246 are preferably used.

The method in which a large part or only a small part of the halogencomposition of silver halide grains is converted by the halogenconversion method is disclosed, for example, in U.S. Pat. Nos. 3,477,852and 4,142,900, European Patent Nos. 273 429 and 273 430, and West GermanPublication Patent No. 3 819 241, and it is an effective method forforming grains. To convert to a more hardly soluble silver salt, it ispossible to add a solution of a soluble halogen or to add silver halidegrains. Selection can be made from respective methods in which theconversion is made at one stroke, in several steps, and continuously.

In addition to the method in which the grain growth is made by adding asoluble silver salt and a halogen salt at constant concentrations and atconstant flow rates, grain formation methods wherein the concentrationis changed or the flow rate is changed, as described in British PatentNo. 1 469 480 and U.S. Pat. Nos. 3,650,757 and 4,242,445, are preferablemethods. By changing the concentration or increasing the flow rate, theamount of the silver halide to be supplied can be changed as a linearfunction, a quadratic function, or a more complex function, of theaddition time. Further, if required, the amount of the silver halide tobe supplied is decreased, which is preferable in some cases. Alsoeffective is an addition method wherein, when several soluble silversalts different in solution composition are added, or when severalsoluble halogen salts different in solution composition are added, oneof them is increased and the other is decreased.

Further, to quicken the growth of the grains, the concentrations, theamounts, and the speeds of the silver salt and the halide to be addedmay be increased (e.g. JP-A-55-142329, JP-A-55-158124, and U.S. Pat. No.3,650,757).

As the method of stirring the reaction liquid, any of known stirringmethods may be used. The temperature and the pH of the reaction liquidduring the formation of the silver halide grains may be set arbitrarilyto meet the purpose. Preferably the pH range is 2.3 to 8.5, and morepreferably 2.5 to 7.5.

A mixing vessel that is used when a solution of a soluble silver saltand a solution of a soluble halogen salt are reacted can be selected foruse from methods described in U.S. Pat. Nos. 2,996,287, 3,342,605,3,415,650, and 3,785,777, and West German Publication Patent Nos. 2 556885 and 2 555 364.

For the purpose of promoting the ripening, a silver halide solvent isuseful. For example, it is known to allow an excess amount of halideions to be present in the reaction vessel, to accelerate the ripening.Further, other ripening agent can be used. All of the amount of theseripening agents may be blended in the dispersion medium in the reactionvessel before silver and halide salts are added, or their introductioninto the reaction vessel may be carried out together with the additionof a halide, a silver salt, or a peptitizer. As another modified mode, amethod is possible wherein a ripening agent is added independently atthe step of adding a halide salt and a silver salt.

In the step for forming grains of the light-sensitive silver halideemulsion for use in the present invention, as a silver halide solvent, arhodanate, ammonia, a tetrasubstituted thioether compound, an organicthioether derivative described in JP-B-47-11386, or a sulfur-containingcompound described in JP-A-53-144319 can be used.

For example, ammonia, thiocyanates (e.g. potassium rhodanate andammonium rhodanate), organic thioether compounds (e.g. compoundsdescribed, for example, in U.S. Pat. Nos. 3,574,628, 3,021,215,3,057,724, 3,038,805, 4,276,374, 4,297,439, 3,704,130, and 4,782,013,and JP-A-57-104926), thion compounds (e.g. tetra-substituted thioureasdescribed, for example, in JP-A-53-82408 and JP-A-55-77737, and U.S.Pat. No. 4,221,863; and compounds described in JP-A-53-144319), mercaptocompounds capable of promoting the growth of silver halide grains, asdescribed in JP-A-57-202531, and amine compounds (e.g. described inJP-A-54-100717), can be mentioned.

As a protective colloid used in the preparation of the emulsion for usein the present invention, and as another binder of the hydrophiliccolloid layer (e.g. structural layers in the heat-developablelight-sensitive material or the dye-fixation material) a hydrophilicbinder is preferably used. Examples thereof include those described inthe above Research Disclosures and on pages (71)-(75) of JP-A-64-13546.Specifically, a transparent or semitransparent hydrophilic binder ispreferred, and gelatin is used advantageously., but another hydrophiliccolloid can also be used.

Use can be made of, for example, a gelatin derivative, a graft polymerof gelatin with another polymer, a protein, such as albumin and casein;a cellulose derivative, such as hydroxycellulose,carboxymethylcellulose, and cellulose sulfate; sodium alginate, a starchderivative, acacia, a saccharide derivative of a natural compound, suchas a polysaccharide, including dextran and pullulan; and many synthetichydrophilic polymers, including homopolymers and copolymers, such as apolyvinyl alcohol, a polyvinyl alcohol partial acetal, apoly-N-vinylpyrrolidone, a polyacrylic acid, a polymethacrylic acid, apolyacrylamide, a polyvinylimidazole, and a polyvinylpyrazole. Further,use can be made of a high-water-absorptive polymer described, forexample, in U.S. Pat. No. 4,960,681 and JP-A-62-245,260, that is, acopolymer of a vinyl monomer having —COOM¹ or —SO₃M¹ (wherein M¹represents a hydrogen atom or an alkali metal), or a copolymer of thesevinyl monomers, or a copolymer of this vinyl monomer with another vinylmonomer (e.g. sodium methacrylate, ammonium methacrylate, and SumikagelL-5H (trade name; manufactured by Sumitomo Chemical Co., Ltd.)). Two ormore of these binders can be used in combination. A combination ofgelatin with any of these binders is also preferable.

As the gelatin, one of lime-processed gelatin, acid-processed gelatin,and so-called de-ashed gelatin wherein the content of calcium or thelike is reduced, can be selected, or a combination of them is alsopreferable. Enzyme-processed gelatin described in Bull. Soc. Sci. Photo.Japan, No. 16, page 30 (1966), may also be used, and a hydrolyzate orenzymolyzate of gelatin can also be used. For the preparation of tabulargrains, it is preferable to use a low-molecular-weight gelatin describedin JP-A-1-158426.

In the case of adopting a system for conducting heat-development withthe supply of a very small amount of water, water can be promptlyabsorbed by using the above-mentioned highly-water-absorbable polymer.In the case that the highly-water-absorbable polymer is used in the dyefixation layer or a protective layer thereof, it is possible to preventthe dye from being re-transferred from the dye fixation element to someother element after transfer.

In the present invention, the application amount of the binder ispreferably 20 g or less, more preferably 10 g or less, and furtherpreferably 7-0.5 g per m².

In the present invention, an organometal salt as an oxidizer may be usedtogether with the light-sensitive silver halide emulsion. Among suchorganometal salts, an organosilver salt is particularly preferably used.

In the case of a heat-developable photographic material, an organosilversalt oxidizing agent may be used together with a photosensitive silverhalide emulsion. As organic compounds capable of being used to form theoxidizing agent, there are benzotriazoles described in U.S. Pat. No.4,500,626, columns 52 to 53, aliphatic acids, and other compounds. Anacetylene silver described in U.S. Pat. No. 4,775,613is also useful. Itis possible to use the organosilver salts in the form of a combinationof two or more.

These organosilver salts are used in an amount of generally 0.01 to 10mol, and preferably 0.01 to 1 mol, per mol of the photosensitive silverhalide. The total coating amount of the photosensitive silver halideemulsion and the organosilver salt is generally 0.05 to 10 g/m², andpreferably 0.1 to 4 g/m², in terms of silver.

Preferably, the silver halide emulsion for use in the present inventionis washed with water for desalting and is dispersed in a freshlyprepared protective colloid. The temperature at which the washing withwater is carried out can be selected in accordance with the purpose, andpreferably the temperature is selected in the range of. 5 to 20° C. ThepH at which the washing is carried out can be selected in accordancewith the purpose, and preferably the pH is selected in the range of 2 to10, and more preferably in the range of 3 to 8. The pAg at which thewashing is carried out can be selected in accordance with the purpose,and preferably the pAg is selected in the range of 5 to 10. As a methodof washing with water, one can be selected from the noodle washingmethod, the dialysis method using a diaphragm, the centrifugationmethod, the coagulation settling method, and the ion exchange method. Inthe case of the coagulation settling method, selection can be made from,for example, the method wherein sulfuric acid salt is used, the methodwherein an organic solvent is used, the method wherein a water-solublepolymer is used, and the method wherein a gelatin derivative is used.Further, the sedimentation method, in which inorganic salts composed ofpolyvalent anions (e.g. sodium sulfate), an anionic surfactant, ananionic polymer (e.g. polystyrenesulfonic acid sodium salt), or agelatin derivative (e.g. an aliphatic-acylated gelatin, anaromatic-acylated gelatin, and an aromatic-carbamoylated gelatin) isemployed, can be used, with the sedimentation method preferred.

The light-sensitive silver halide emulsion is generally achemically-sensitized silver halide emulsion. To chemically sensitizethe light-sensitive silver halide emulsion for use in the presentinvention, for example, a chalcogen sensitization method, such as asulfur sensitization method, a selenium sensitization method, and atellurium sensitization method; a noble metal sensitization method,wherein gold, platinum, or palladium is used; and a reductionsensitization method, each of which is known for silver halide emulsionsin light-sensitive material, can be used alone or in combination (e.g.JP-A-3-110555 and JP-A-5-241267). These chemical sensitizations can becarried out in the presence of a nitrogen-containing heterocycliccompound (JP-A-62-253159). Further, the below-mentioned antifoggant canbe added after the completion of the chemical sensitization.Specifically, methods described in JP-A-5-45833 and JP-A-62-40446 can beused.

At the time of the chemical sensitization, the pH is preferably 5.3 to10.5, and more preferably 5.5,to 8.5, and the pAg is preferably 6.0 to10.5, and more preferably 6.8 to 9.0.

The coating amount of the light-sensitive silver halide emulsion used inthe present invention is generally in the range of 1 mg to 10 g/m² interms of silver, and preferably in the range of 10 mg to 10 g/m².

When the emulsion according to the present invention is prepared, inaccordance with the purpose, it is preferable to allow a salt of a metalion to be present, for example, at the time when grains are formed, inthe step of desalting, at the time when the chemical sensitization iscarried out, or before the application. When the grains are doped, theaddition is preferably carried out at the time when the grains areformed; or after the formation of the grains, when the surface of thegrains is modified or when the salt of a metal ion is used as a chemicalsensitizer; or before the completion of the chemical sensitization. Asto the doping of grains, selection can be made from a case in which thewhole grains are doped, one in which only the core parts of the grainsare doped, one in which only the shell parts of the grains are doped,one in which only the epitaxial parts of the grains are doped, and onein which only the substrate grains are doped. For example, Mg, Ca, Sr,Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os,Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb, and Bi can be used. These metals canbe added if they are in the form of a salt that is soluble at the timewhen grains are formed, such as an ammonium salt, an acetate, a nitrate,a sulfate, a phosphate, a hydroxide, a six-coordinate complex, and afour-coordinate complex. Examples include CdBr₂, CdCl₂, Cd(NO₃)₂,Pd(NO₃)₂, Pb(CH₃COO)₂, K₃[Fe(CN)₆], (NH₄)₄[Fe(CN)₆], K₃IrCl₆,(NH₄)₃RhCl₆, and K₄Ru(CN)₆. As a ligand of the coordinationcompound,-one can be selected from halo, aquo, cyano, cyanate,thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. With respect tothese metal compounds, only one can be used, but two or more can also beused in combination.

In some cases, a method wherein a chalcogen compound is added during thepreparation of the emulsion, as described in U.S. Pat. No. 3,772,031, isalso useful. In addition to S, Se, and Te, a cyanate, a thiocyanate, aselenocyanate, a carbonate, a phosphate, or an acetate may be present.

The silver halide grains according to the present invention can besubjected to at least one of sulfur sensitization, seleniumsensitization, tellurium sensitization (these three are called chalcogensensitization, collectively), noble metal sensitization, and reductionsensitization, in any step of the production for the silver halideemulsion. A combination of two or more sensitizations is preferable.Various types of emulsions can be produced, depending on the steps inwhich the chemical sensitization is carried out. There are a typewherein chemical sensitizing nuclei are embedded in grains, a typewherein chemical sensitizing nuclei are embedded at parts near thesurface of grains, and a type wherein chemical sensitizing nuclei areformed on the surface. In the emulsion according to the presentinvention, the location at which chemical sensitizing nuclei aresituated can be selected in accordance with the purpose, and generallypreferably at least one type of chemical sensitizing nucleus is formednear the surface.

Chemical sensitizations that can be carried out preferably in thepresent invention are chalcogen sensitization and noble metalsensitization, which may be used singly or in combination; and thechemical sensitization can be carried out by using active gelatin asdescribed by T. H. James in “The Photographic Process,” 4th edition,Macmillan, 1997, pages 67 to 76, or by using sulfur, selenium,tellurium, gold, platinum, palladium, or iridium, or a combination ofthese sensitizing agents, at a pAg of 5 to 10, a pH of 5 to 8, and atemperature of 30 to 80° C., as described in Research Disclosure, Item12008 (April 1974); Research Disclosure, Item 13452 (June 1975);Research Disclosure, Item 307105 (November 1989); U.S. Pat. Nos.2,642,361, 3,297,446, 3,772,031, 3,857,711, 3,901,714, 4,266,018, and3,904,415, and British Patent No. 1 315 755.

In the sulfur sensitization, an unstable sulfur compound is used, andspecifically, thiosulfates (e.g. hypo), thioureas (e.g.diphenylthiourea, triethylthiourea, and allylthiourea), rhodanines,mercaptos, thioamides, thiohydantoins, 4-oxooxazolidin-2-thions, di- orpoly-sulfides, polythionic acids, and elemental sulfur, and knownsulfur-containing compounds described in U.S. Pat. Nos. 3,857,711,4,266,018, and 4,054,457, can be used. In many cases, sulfursensitization is used in combination with noble metal sensitization.

A preferable amount of a sulfur sensitizing agent used for the silverhalide grains according to the present invention is 1×10⁻⁷ to 1×10⁻³mol, and more preferably 5×10⁻⁷ to 1×10⁻⁴ mol, per mol of the silverhalide.

In the selenium sensitization, known unstable selenium compounds areused, such as those described, for example, in U.S. Pat. Nos. 3,297,446and 3,297,447, specific such selenium compounds are colloidal metalselenium, selenoureas (e.g. N,N-dimethylselenourea andtetramethylselenourea), selenoketones (e.g. selenoacetone), selenoamides(e.g. selenoacetamide), selenocarboxylic acids and esters,isoselenocyanates, selenides (e.g. diethylselenides andtriphenylphosphine selenide), and selenophosphates (e.g.tri-p-tolylselenophosphate). In some cases, preferably the seleniumsensitization is used in combination with one or both of sulfursensitization and noble metal sensitization.

The amount of the selenium sensitizing agent to be used varies dependingon the selenium compound, the silver halide grains, the chemicalripening conditions, and the like that are used, and the amount isgenerally of the order of 10⁻⁸ to 10⁻⁴ mol, and preferably 10⁻⁷ to 10⁻⁵mol, per mol of the silver halide.

As the tellurium sensitizing agent used in the present invention,compounds described in Canadian Patent No. 800 958, British Patent Nos.1 295 462 and 1 396 696, JP-A-4-204640 and JP-A-4-333043 can be used,and specific tellurium sensitizing agents include colloidal tellurium,telluroureas (e.g. tetramethyltellurourea,N-carboxylethyl-N′,N′-dimethyltellurourea, andN,N′-dimethylethylenetellurourea), isotellurocyanates, telluroketones,telluroamides, tellurohydrazides, telluroesters, phosphine tellurides(e.g. tributylphosphine telluride and butylisopropylphosphinetelluride), and other tellurium compounds (e.g. potassium tellurocyanateand sodium telluropentathionate).

The amount of the tellurium sensitizing agent to be used is of the orderof generally 10⁻⁷ to 5×10⁻² mol, and preferably 5×10⁻⁷ to 10⁻³ mol, permol of the silver halide.

In the noble metal sensitization, a salt of a noble metal, such asplatinum, gold, palladium, and iridium, can be used, and specificallygold sensitization, palladium sensitization, and a combination thereofare particularly preferable. In the case of gold sensitization, a knowncompound, such as chloroauric acid, potassium chloroaurate, potassiumauriothiocyanate, gold sulfide, and gold selenide, can be used. Thepalladium compound means a salt of divalent or tetravalent palladiumsalt. A preferable palladium compound is represented by R¹¹ ₂PdX³ ₆ orR¹¹ ₂PdX³ ₄, wherein R¹¹ represents a hydrogen atom, an alkali metalatom, or an ammonium group; and X³ represents a halogen atom, i.e. achlorine atom, a bromine atom, or an iodine atom.

Specifically, K₂PdCl₄, (NH₄)₂PdCl₆, NaPdCl₄, (NH₄)₂PdCl₄, Li₂PdCl₄,Na₂PdCl₆, or K₂PdBr₄ is preferable. Preferably a gold compound and apalladium compound are used in combination with a thiocyanate or aselenocyanate.

Preferably the emulsion according to the present invention is used incombination with gold sensitization. A preferable amount of the goldsensitizing agent is 1×10⁻⁷ to 1×10⁻³ mol, and more preferably 5×10⁻⁷ to5×10⁻⁴ mol, per mol of the silver halide. A preferable amount of thepalladium compound is in the range of 5×10⁻⁷ to 1×10⁻³ mol. A preferableamount of the thiocyan compound and the selenocyan compound is in therange of 1×10⁻⁶ to 5×10⁻² mol.

Preferably that the silver halide emulsion according to the presentinvention is subjected to reduction sensitization during the formationof the grains, after the formation of the grains but before the chemicalsensitization, or during or after the chemical sensitization.

Herein, the reduction sensitization can be selected from a methodwherein a reduction sensitizer is added to a silver halide emulsion; amethod called silver ripening, wherein the growth or ripening is made inan atmosphere having a pAg as low as 1 to 7; and a method called high-pHripening, wherein the growth or ripening is made in an atmosphere havinga pH as high as 8 to 11. Two or more methods can also be used incombination.

The method wherein a reduction sensitizer is added is preferable,because the level of reduction sensitization can be adjusted subtly.

As the reduction sensitizer, known reduction sensitizers can be selectedand used, such as stannous salts, ascorbic acid and its derivatives,amines and polyamines, hydrazine and its derivatives, formamidinesufinicacid, silane compounds, and boran compounds; and two or more compoundscan be used in combination. As the reduction sensitizer, preferablecompounds are stannous chloride, aminoiminomethanesulfinic acid(popularly called thiourea dioxide), dimethylamineboran, and ascorbicacid and its derivatives. Since the amount of the reduction sensitizerto be added depends on the conditions of the production of the emulsion,the amount must be selected, but preferably it is in the range of 10⁻⁷to 10⁻³ mol per mol of the silver halide.

The chemical sensitization can be carried out in the presence of aso-called chemical sensitization auxiliary. As a useful chemicalsensitization auxiliary, a compound is used that is known to suppressfogging and to increase the sensitivity in the process of chemicalsensitization, such as azaindene, azapyridazine, and azapyrimidine.Examples of chemical sensitization auxiliary improvers are described inU.S. Pat. Nos. 2,131,038, 3,411,914, and 3,554,757, JP-A-58-126526, andby G. F. Duffin in “Photographic Emulsion Chemistry” mentioned above,pages 138 to 143.

Preferably, an oxidizing agent for silver is added during the process ofthe production of the emulsion according to the present invention. Theoxidizing agent for silver refers to a compound that acts on metalsilver to convert it to silver ions. Particularly useful is a compoundthat converts quite fine silver grains, which are concomitantly producedduring the formation of silver halide grains and during the chemicalsensitization, to silver ions. The thus produced silver ions may form asilver salt that is hardly soluble in water, such as a silver halide,silver sulfide, and silver selenide, or they may form a silver salt thatis readily soluble in water, such as silver nitrate. The oxidizing agentfor silver may be inorganic or organic. Example inorganic oxidizingagents include ozone, hydrogen peroxide and its adducts (e.g. NaBO₂,H₂O₂.H₂O, 2NaCO₃.H₂O₂, Na₄P₂O₇.H₂O₂, and 2NaSO₄.H₂O₂.2H₂O); oxygen acidsalts, such as peroxyacid salts (e.g. K₂S₂O₈, K₂C₂O₆, and K₂P₂O₈),peroxycomplex compounds (e.g. K₂[Ti(O₂)C₂O₄].3H₂O, 4K₂SO₄.Ti(O₂)OH.SO₄.2H₂O, and Na₃[VO(O₂)(C₂O₄)₂].6H₂O), permanganates (e.g. KMnO₄), andchromates (e.g. K₂CrO₇); halogen elements, such as iodine and bromine;perhalates (e.g. potassium periodate), salts of metals having highervalences (e.g. potassium hexacyanoferrate(III) and thiosulfonates.

Examples of the organic oxidizing agents include quinones, such asp-quinone; organic peroxides, such as peracetic acid and perbenzoicacid; and compounds that can release active halogen (eg.N-bromosuccinimido, chloramine T, and chloramine B).

Preferable oxidizing agents used in the present invention are suchinorganic oxidizing agents as ozone, hydrogen peroxide and its adducts,halogen elements, and thiosulfonates, and such organic oxidizing agentsas quinones. Use of a combination of the above reduction sensitizationwith the oxidizing-agent for silver is a preferable mode. Use is made ofone selected from a method wherein after an oxidizing agent is used,reduction sensitization is carried out; a method where in afterreduction sensitization is carried out, an oxidizing agent is used; anda method wherein an oxidizing agent and a reduction sensitizer arepresent simultaneously. These methods can be used in the step of forminggrains or in the step of chemical sensitization, which step will bechosen.

In the photographic emulsion used in the present invention, variouscompounds can be incorporated for the purpose of preventing foggingduring the process of the production of the photographic material,during the storage of the photographic material, or during thephotographic processing, or for the purpose of stabilizing thephotographic performance. That is, various compounds known asantifoggants or stabilizers can be added, such as thiazoles includingbenzothiazolium salts, nitroimidazoles, nitrobenzimidazoles,chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles,aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles(particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidine,mercaptotriazine; thioketo compounds, such as oxazolinthione; andazaindenes, such as triazaindenes; tetraazaindenes (particularly4-hydroxy-6-methyl-1,3,3a,7-tetraazaindenes), and pentaazaindenes. Forexamples, those described in U.S. Pat. Nos. 3,954,474 and 3,982,947, andJP-B-62-28660, can be used. A preferable compound is a compounddescribed in JP-A-63-212932. In accordance with the purpose, theantifoggant and the stabilizer can be added at various times, forexample, before the formation of the grains, during the formation of thegrains, after the formation of the grains, in the step of washing withwater, at the time of dispersion after the washing with water, beforethe chemical sensitization, during the chemical sensitization, after thechemical sensitization, and before the application. In addition to thecase wherein the antifoggant and the stabilizer are added during thepreparation of the emulsion, so that the antifogging effect and thestabilizing effect, which are their essential effects,may be achieved,they can be used for various other purposes, for example, forcontrolling the habit of the crystals of the grains, for making thegrain size small, for reducing the solubility of the grains, forcontrolling the chemical sensitization, and for controlling thearrangement of the dyes.

When the photosensitive silver halide used in the present invention ismade to have color sensitivities of green sensitivity, red sensitivity,and infrared sensitivity, the photosensitive silver halide emulsion isgenerally spectrally sensitized with methine dyes or the like. Ifrequired, the blue-sensitive emulsion may be spectrally sensitized inthe blue region.

Dyes that can be used include a cyanine dye, a merocyanine dye, acomposite cyanin dye, a composite merocyanine dye, a halopolar cyaninedye, a hemicyanine dye, a styryl dye, and a hemioxonol dye. Particularlyuseful dyes are those belonging to a cyanine dye, a merocyanine dye, anda composite merocyanine dye. In these dyes, any of nuclei generally usedin cyanine dyes as basic heterocycle nuclei can be applied. That is, apyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrolenucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus,an imidazole nucleus, a tetrazole nucleus, and a pyridine nucleus; and anucleus formed by fusing an cycloaliphatic hydrocarbon ring or anaromatic hydrocarbon ring to these nuclei, that is, 5- to 6-heterocyclenuclei, such as an indolenine nucleus, a benzindolenine nucleus, anindole nucleus, a benzoxazole nucleus, a naphthooxazole nucleus, abenzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazolenucleus, a benzimidazole nucleus, a rhodanine nucleus, and athiobarbituric acid nucleus, can be applied. These nuclei may besubstituted on the carbon atom. Specifically, sensitizing dyesdescribed, for example, in U.S. Pat. No. 4,617,257 and JP-A-59-180550,JP-A-64-13546, JP-A-5-45828, and JP-A-5-45834 can be mentioned.

In the merocyanine dye or the composite merocyanine dye, as a nucleushaving a ketomethylene structure, a 5-to 6-membered heterocycle nucleus,such as a pyrazolin-5-one nucleus, a thiohydantoine nucleus, a2-thiooxazolidin-2,4-dione nucleus, a thiazolidin-2,4-dione nucleus, arhodanine nucleus, and a thiobarbituric acid nucleus, can be applied.

These dyes can be used singly or in combination, and a combination ofthese sensitizing dyes is often used, particularly for the purpose ofadjusting the wavelength of the spectral sensitivity, and for thepurpose of supersensitization. Typical examples thereof are described inU.S. Pat. Nos. 2,688,545, 3,397,060, 2,977,229, 3,522,052, 3,527,64,3,617,293, 3,628,964, 3,672,989, 3,679,428, 3,703,377, 3,769,301,3,814,609, 3,837,862, and 4,026,707, British Patent Nos. 1 344 218 and 1507 803, JP-B-43-4936, JP-B-53-12375, JP-A-52-110618 and JP-A-52-109925.

Together with the sensitizing dye, a dye having no spectral sensitizingaction itself, or a compound that does not substantially absorb visiblelight and that exhibits supersensitization, may be included in theemulsion (e.g. those described, for example, in U.S. Pat. No. 3,615,641and JP-A-63-23145).

The time when these sensitizing dyes are added to the emulsion may be atany stage of the preparation of the emulsion that is known to be useful,for example, at chemical ripening, or before or after chemical ripening.

Most usually, the sensitizing dye is added at a time after thecompletion of chemical sensitization but before the application, but thesensitizing dye may be added at the same time as the addition of thechemical sensitizer, to carry out spectral sensitization and chemicalsensitization simultaneously, as described in U.S. Pat. Nos. 3,628,969and 4,225,666, or the sensitizing dye may be added before the chemicalsensitization, as described in JP-A-58-113928. Further, the sensitizingdye may be added before the completion of the precipitation of thesilver halide grains, to start the spectral sensitization. Further, thesensitizing dye may be added before or after the formation of nuclei ofthe silver halide grains, in accordance with U.S. Pat. Nos. 4,183,756and 4,225,666, or it may be added in portions, such that part of thesensitizing dye is added before the chemical sensitization, and the restis added after the chemical sensitization.

Further, these sensitizing dyes and supersensitizing dyes may be addedin the form of a solution of an organic solvent, such as methanol, or inthe form of a dispersion of gelatin, or in the form of a solution of asurface-active agent.

Generally the amount of the sensitizing dye to be added is of the orderof 4×10⁻⁶ to 8×10⁻³ mol per mol of the silver halide, but when thesilver halide grain size is 0.2 to 1.2 μm, which is more preferable, theamount of the sensitizing dye to be added is more effectively about5×10⁻⁵ to 2×10⁻³ mol per mol of the silver halide.

As the reducing agent that can be used in the present invention, areducing agent known in the field of heat-developable light-sensitivematerial may be used. The known reducing agent may be a dye-providingcompound having a reducing ability, which will be described later. Inthis case, some other reducing agent may also be used at the same time.A reducing agent precursor, which exhibits no reducing ability byitself, but exhibits reducing ability by the action of a nucleophilicagent or heat during the step of development may be used.

Examples of the reducing agent or the precursor thereof for use in thepresent invention include those described in U.S. Pat. No. 4,500,626,col. 49-50, U.S. Pat. Nos. 4,839,272, 4,330,617, 4,590,152, 5,017,454and 5,139,919, JP-A-60-140335, pages (17)-(18), JP-A-57-40245,JP-A-56-138736, JP-A-59-178458, JP-A59-53831, JP-A-59-182449,JP-A-59-182450, JP-A-60-119555, JP-A-60-128436, JP-A-60-128439,JP-A-60-198540, JP-A-60-181742, JP-A-61-259253, JP-A-62-201434,JP-A-62-244044, JP-A-62-131253, JP-A-62-131256, JP-A-63-10151,JP-A-64-13546, pages (40)-(57), JP-A-1-120553, JP-A-2-32338,JP-A-2-35451, JP-A-2-234158 and JP-A-3-160443, and EP Patent No.220,746, pages 78-96.

Combinations of various reducing agents can also be used, as disclosedin U.S. Pat. No. 3,039,869.

In the case that a reducing agent having nondiffusibility is used, acombination of an electron-transferring agent and/or anelectron-transferring agent precursor with the nondiffusion reducingagent may be optionally used, to accelerate electron-movement betweenthe nondiffusion reducing agent and silver halide that is developable.It is particularly preferred to use the electron-transferring agent orthe precursor described in the U.S. Pat. No. 5,139,919, EP-A-418,743,JP-A-1-138556 and JP-A-3-102345. It is preferred to use a method ofintroducing the agent or the precursor stably into a given layer, asdescribed in JP-A-2-230143 and JP-A-2-235044.

The electron-transferring agent or the precursor thereof can be selectedamong the above-mentioned reducing agents or the precursors thereof. Theelectron-transferring agents or the precursor thereof preferably has alarger mobility than the nondiffusion reducing agent (electron-providingmaterial). A particularly useful electron-transferring agent is any oneof 1-phenyl-3-pyrazolidones and aminophenols.

The nondiffusion reducing agent (electron-donating material), which iscombined with the electron-transferring agent so as to be used, may beany one of the above-mentioned reducing agents which do not movesubstantially in layers of the light-sensitive material. Preferredexamples thereof include hydroquinones; sulfoneamidephenols;sulfoneamidenaphthols; compounds described as electron donatingmaterials in JP-A-53-110827, U.S. Pat. Nos. 5,032,487, 5,026,634 and4,839,272; and dye-providing compounds having nondiffusibility andreducing ability, which will be described later.

It is also preferred to use an electron-providing material precursor asdescribed in JP-A-3-160443.

The above-mentioned reducing agent can be used in the intermediate layerand the protective layer for various purposes, such as prevention tocolor mixture, improvement in color reproduction and whiteness,prevention of silver-transfer to the dye fixation material.Specifically, it is preferred to use a reducing agent described inEP-A-524,649 and 357,040, JP-A-4-249245, JP-A-2-64633, JP-A-2-46450 andJP-A-63-186240. It is also possible to use a development restrainerreleasing, reducible compound as described in JP-B-3-63733,JP-A-1-150135, JP-A-2-110557, JP-A-2-64634 and JP-A-3-43735, andEP-A-451,833.

In the present invention, the total addition amount of the reducingagent is generally 0.01-20 moles and particularly preferably 0.1-10moles per mole of silver.

To the photographic material related to the present technique, may beadded the above-mentioned various additives, and also other variousadditives in accordance with the purpose.

These additives and conventionally known additives for photography thatcan be used in dye-fixing materials and heat-developable-light-sensitivematerials of the present invention, are described in more detail inResearch Disclosure, Item 17643 (December 1978); Research Disclosure,Item 18176 (November 1979); and Research Disclosure, Item 307105(November 1989), and the particular parts are given below in a table.

RD Additive 17643 RD 18716 RD 307105 1 Chemical p.23 p.648 (right p.996sensitizers column) 2 Sensitivity- — p.648 (right — enhancing agentscolumn) 3 Spectral pp.23-24 pp.648 (right pp.996-998 sensitizers andcolumn)-649 Supersensitizers (right column) 4 Brightening p.24 pp.647(right p.998 agents column) 5 Light absorbers, pp.25-26 pp.649 (rightp.1003 Filter dyes, and column)-650 UV Absorbers (left column) 6 Bindersp.26 p.651 pp.1003-1004 7 Plasticizers and p.27 p.650 p.1006 Lubricants8 Coating aids and pp.26-27 p.650 pp.1005 Surfactants (left)-1006(right) 9 Antistatic p.27 p.650 (right pp.1006-1007 agents column) 10Antifogging pp.24-25 p.649 pp.998-1000 agents and Stabilizers 11Anti-staining p.25 p.650 (left to agents (right right) column) 12Image-dye p.25 p.650 (left p.872 stabilizers column) 13 Hardeners p.26p.651 (left pp.1004 column) (right)-1005 (left) 14 Matt agent — —pp.878-879

In addition to the above hardeners, other hardeners described, forexample, in U.S. Pat. No. 4,678,739, 41st column; U.S. Pat. No.4,791,042, and JP-A-59-116655, JP-A-62-245261, JP-A-61-18942, andJP-A-4-218044, can be mentioned. More specifically, aldehyde hardeners(e.g. formaldehyde), aziridine hardeners, epoxy hardeners, vinyl sulfonehardeners (e.g. N,N′-ethylene-bis(vinylsulfonylacetamide)ethane),N-methylol hardeners (e.g. dimethylol urea), or polymer hardeners (e.g.compounds described, for example, in JP-A-62-234157) can be mentioned.

These hardeners are used in an amount of generally 0.001 to 1 g, andpreferably 0.005 to 0.5 g, per g of the coated gelatin. The layer intowhich the hardener(s) is added may be any of layers that constitute thephotographic material (another name, a photographic element) or thedye-fixing material (another name, a dye-fixing element or animage-receiving element), or the hardener may be divided into two ormore parts, which are added into two or more layers.

In the dye-fixing material and the photographic material of the presentinvention, a matting agent can be used for the purpose of adhesionprevention, improvement of slipping property, matting, and the like.Example matting agents include silicon dioxide, polyolefins,polymethacrylates, and the like described in JP-A-61-88256, page (29),as well as compounds, including benzoguanamine resin beads,polycarbonate resin beads, ABS resin beads, and the like, described inJP-A-63-274944 and JP-A-63-274952. Other matting agents described in theabove RDs can be used. These matting agents are added into the uppermostlayer (protective layer), and also into a lower layer if required.

Further, the constitutional layers of a heat-developable photographicmaterial and dye-fixing material may contain a heat solvent, anantifoaming agent, an anti-bacterial agent, a mildew-proofing agent,colloidal silica, and the like. Specific examples of these additives aredescribed, for example, in JP-A-61-88256, pages (26) to (32);JP-A-3-11338, and JP-B-2-51496.

In the constitutional layers of the dye-fixing material and thephotographic material of the present invention, use can be made ofvarious surface-active agents for various purposes of, for example,serving as a coating aid, improving releasability and slipping property,preventing electrification (static), or accelerating development.Specific examples of the surface-active agents are described, forexample, in the above Research Disclosures and JP-A-62-173463 andJP-A-62-183457. In the case of a heat-developable photographic materialand a dye-fixing material, also preferably an organofluoro-compound iscontained in the constitutional layer, for example, for the purposes ofimproving slipping properties, preventing electrification, and improvingreleasability. Typical examples of the organofluoro compound arehydrophobic fluorine-containing compounds, including solid fluorocompound resins, such as ethylene tetrafluoride resins; oily fluorocompounds, including fluoro oils; or fluorine-containing surface-activeagents described, for example, in JP-B-57-9053, 8th column to the 17thcolumn, and JP-A-61-20944 and JP-A-62-135836.

In the photographic material of the present invention, known antifadingagents can be used. Example organic antifading agents includehydroquinones, 5-hydroxychromans, 5-hydroxycoumarans, paraalkoxyphenols,hindered phenols, including bisphenols; gallic acid derivatives,methylenedioxybenzenes, aminophenols, hindered amines, and ether orester derivatives produced by silylating or alkylating the phenolichydroxyl group of these compounds. Further, metal complexes, representedby (bissalicylaldoximato)nickel complex and (bis-N,N-dialyldithiocarbamato)nickel complex, can also be used.

To prevent a yellow dye image from being deteriorated by heat, humidity,and light, the addition of a compound having both the structures of ahindered amine and a hindered phenol in the same molecule, as describedin U.S. Pat. No. 4,268,593, gives a good result. Further, to prevent amagenta dye image from being deteriorated particularly by light,spiroindanes described in JP-A-56-159644, and chromans substituted witha hydroquinone diether or monoether, described in JP-A-55-89835, give agood result.

In the constitutional layers of the dye-fixing material and thephotographic material of the present invention, various antifoggants orphotographic stabilizers and their precursors can be used. Specificexamples thereof include compounds described, for example, in theabove-mentioned Research Disclosures, U.S. Pat. Nos. 5,089,378,4,500,627, and 4,614,702, JP-A-64-13546 (pages (7) to (9), (57) to (71),and (81) to (97)), U.S. Pat. Nos. 4,775,610, 4,626,500, and 4,983,494,JP-A-62-174747, JP-A-62-239148, JP-A-63-264747, JP-A-1-150135,JP-A-2-110557, and JP-A-2-178650, and Research Disclosure No. 17 643(1978), pages (24) to (25).

These compounds are preferably used in an amount of 5×10⁻⁶ to 1×10⁻¹mol, and more preferably 1×10⁻⁵×1×10⁻² mol, per mol of silver.

Suitable support (base) that can be used-in the present inventioninclude a synthetic plastic film, for example, made of polyolefins, suchas polyethylene and polypropylene, polycarbonates, cellulose acetates,polyethylene terephthalates, polyethylene naphthalates, and polyvinylchlorides; a paper support, for example, made of photographic raw paper,printing paper, baryta paper, and resin-coated paper; a support formedby providing the above plastic film with a reflective layer; and asupport described in JP-A-62-253159, pages 29 to 31.

Those described in the above Research Disclosure No. 17643, page28;Research,Disclosure No. 18716, page 647, right column, to page 648, leftcolumn; and Research Disclosure No. 307105, page 879, are alsopreferably used. These supports may be subjected to heat treatment at orbelow Tg, as described in U.S. Pat. No. 4,141,735, so that they may behardly core-set. The surface of the support may be surface-treated, toimprove the adhesion between the support and the emulsion undercoatlayer. In the present invention, the surface treatment can be carriedout by glow discharge treatment, ultraviolet-ray-irradiation treatment,corona treatment, or flame treatment.

Further, supports described in Kochi Gijutsu No. 5 (published byAzutekku Yugen-kaisha, Mar. 22, 1991), pages 44 to 149, can also beused.

Transparent supports made, for example, of polyethylenenaphthalenedicarboxylates, and supports produced by coating these transparentsupports with a transparent magnetic substance, can also be used.

In a heat-developable photographic material, in order to obtain aconstant image all the time against changes in the processingtemperature and the processing time at the time of development, variousdevelopment inhibitors can be used. Herein, the term “a developmentinhibitor” means a compound that neutralizes bases quickly or reactsquickly with bases after suitable development, to lower the baseconcentration in the film, to stop the development; or a compound thatinteracts with silver and silver salts, to inhibit the development.Specific examples include acid precursors that release an acid whenheated, electrophilic compounds that undergo a substitution reactionwith coexisting bases when heated; and nitrogen-containing heterocycliccompounds, mercapto compounds, and their precursors. Details aredescribed in JP-A-62-253159, pages (31) to (32).

When the photographic material of the present invention is used as aheat-developable photographic material; to supply a base, a methodwherein a base is generated from a base precursor, is preferable.

Preferable base precursors that can be used in the present inventioninclude a salt of a base with an organic acid that is decarboxylatedwhen heated; a compound that is decomposed by such a reaction as anintramolecular nucleophilic substitution reaction, Lossen rearrangement,or Beckmann rearrangement, to release amines; a compound that undergoessome reaction when heated, to release a base; and a compound thatundergoes hydrolysis or a complex formation reaction, to generate abase. Examples of the above base precursor that generates a base whenheated include salts of trichloroacetic acid described, for example, inBritish Patent No. 998 959; salts of α-sulfonylacetic acid that arefurther improved in stability, as described in U.S. Pat. No. 4,060,420;salts of propiolic acid described in JP-A-59-180537; 2-carboxycarboamidederivatives described in U.S. Pat. No. 4,088,496; salts ofheat-decomposable acids that are formed using, in addition to an organicbase, an alkali metal or an alkali earth metal as a base component(JP-A-59-195237); hydroxamcarbamates that use Lossen rearrangement, asdescribed in JP-A-59-168440; and aldoximecarbamates that produce nitrilewhen heated, as described in JP-A-59-157637.

Also useful are base precursors described, for example, in BritishPatent Nos. 998 945 and 2 079 480, JP-A-50-226225, U.S. Pat. Nos.3,220,846, 4,514,493, and 4,657,848, and Kochi Gijutsu No. 5 (publishedby Azutekku Yugen-kaisha, Mar. 22, 1991), pages 55 to 86.

Examples of the method of exposing the photographic material of thepresent invention with light and recording the image, include a methodwherein a landscape, a man, or the like is directly photographed by acamera or the like; a method wherein a reversal film or a negative filmis exposed to light using, for example, a printer, or an enlargingapparatus; a method wherein an original picture is subjected to scanningexposure through a slit by using an exposure system of a copying machineor the like; a method wherein light-emitting diodes and various lasers(e.g. laser diodes and gas lasers) are allowed to emit light, to carryout scanning exposure through image information-and electrical signals(methods described, for example, in JP-A-2-129625, JP-A-5-176144,JP-A-5-199372, and JP-A-6-127021); and a method wherein imageinformation is outputted to an image display device, such as a CRT, aliquid crystal display, an electroluminescence display, and a plasmadisplay, and exposure is carried out directly or through an opticalsystem.

Light sources that can be used for recording an image on thephotographic material, as mentioned above, include natural light andlight sources and exposure methods described in U.S. Pat. No. 4,500,626,56th column, and JP-A-2-53378 and JP-A-2-54672, such as a tungsten lamp,a light-emitting diode, a laser light source, and a CRT light source.

Image-wise exposure can be carried out by using a wavelength-convertingelement that uses a nonlinear optical material and a coherent lightsource, such as laser rays, in combination. Herein the term “nonlinearoptical material” refers to a material that can develop nonlinearity ofthe electric field and the polarization that appears when subjected to astrong photoelectric field, such as laser rays, and inorganic compounds,represented by lithium niobate, potassium dihydrogenphosphate (KDP),lithium iodate, and BaB₂O₄; urea derivatives, nitroaniline derivatives,nitropyridine-N-oxide derivatives, such as3-methyl-4-nitropyridine-N-oxide (POM); and compounds described inJP-A-61-53462 and JP-A-62-210432 can be preferably used. As the form ofthe wavelength-converting element, for example, a single crystal opticalwaveguide type and a fiber type are known, both of which are useful.

The above image information can employ, for example, image signalsobtained from video cameras, electronic still cameras, and the like;television signals, represented by Nippon Television Singo Kikaku(NTSC); image signals obtained by dividing an original picture into anumber of picture elements by a scanner or the like; and an imageproduced by a computer, represented by CG or CAD.

The color-developing agent of the present invention can be used for allsilver halide photographic materials, including color negatives, colorpapers, X-ray photographic materials and photomechanical reproductionmaterials for color instant photography and color reversal, and X-rayphotographic materials and reproduction photographic materials forforming color images. Further, the color-developing agent of the presentinvention can be added into a silver halide photographic material, andalso into a processing solution. The color-developing agent of thepresent invention can be preferably contained in at least onehydrophilic colloid layer provided on a support, when it is used in asilver halide light-sensitive material. As a silver halidelight-sensitive material containing the color-developing agent of thepresent invention, a color diffusion transfer silver halide photographiclight-sensitive material is preferable.

When the color-developing agent of the present invention is added into asilver halide photographic material, the development can be carried outby heating treatment or activator treatment.

The heating treatment of photographic materials is known in the art, andheat-developable photographic materials and the process thereof aredescribed, for example, in “Shashin Kogaku no Kiso” (published byCoronasha, 1979), pages 553 to 555; “Eizo Joholl” (published on April1978), page 40; “Nebletts Handbook of Photography and Reprography,” 7thedition (Van Nostrand and Reinhold Company), pages 32 to 33; U.S. Pat.Nos. 3,152,904, 3,301,678, 3,392,020, and 3,457,075, British Patent Nos.1 131 108 and 1 167 777, and Research Disclosure (June 1978), pages 9 to15 (RD-17029).

The activator treatment refers to a treatment wherein a color-developingagent is built in a photographic material and the photographic materialis subjected to development with a processing solution free from anycolor-developing agent. In this case, the processing solution ischaracterized in that it does not contain any color-developing agent,which is usually contained as a development processing solutioncomponent, but the processing solution may contain other components(e.g. an alkali and an auxiliary developing agent). Examples of theactivator treatment are shown in known publications, such asEuropean-Patent-Nos. 545 491(A1) and 565 165(A1).

In the present invention, the term “a developing solution” means aprocessing solution containing a color-developing agent or a processingsolution not containing a developing agent (for activator).

The processing temperature of the developing solution to be applied tothe present invention is generally 20 to 50° C., and preferably 30 to45° C. The processing time is generally 5 sec to 2 min, and preferably10 sec to 1 min. With respect to the replenishing rate, although a smallamount is preferable, the replenishing rate is generally 15 to 600 ml,preferably 25 to 200 ml, and more preferably 35 to 100 ml, per m² of thephotographic material to be processed.

The photographic material of the present invention may be in a formhaving an electro-conductive heat-generating element layer, which servesas a heating means for heat processing. In this case, as theheat-generating element, those described, for example, in JP-A-61-145544can be employed.

The heating temperature in the heat development step is generally about65 to 180° C., preferably 70 to 180° C., more preferably 75 to 180° C.,further more preferably 80 to 150° C., and particularly preferably 80 to135° C. The heating time is preferably 0.1 to 120 sec, more preferably0.1 to 60 sec and particularly preferably 0.1 to 30 sec.

Example heating methods in the development step and/or transferring stepinclude one wherein the photographic material is brought in contact witha heated block or plate; a method wherein the photographic material isbrought in contact with a hot plate, a hot presser, a hot roller, a hotdrum, a halogen lamp heater, an infrared lamp heater, or a far-infraredlamp heater; and a method wherein the photographic material is passedthrough a high-temperature atmosphere. As a method wherein theheat-developable photographic material and a dye-fixing material areplaced one upon the other, methods described in JP-A-62-253159 andJP-A-61-147244, on page (27) can be applied.

After the development, a desilvering process can be carried out. Thedesilvering process comprises a fixing process, or both bleachingprocess and a fixing process. When both bleaching and fixing are carriedout, the bleaching process and the fixing process may be carried outseparately or simultaneously (bleach-fixing process). Also, according tothe purpose, the processing may be carried out in a bleach-fixing bathhaving two successive tanks; or the fixing process may be carried outbefore the bleach-fixing process; or the bleach-fixing may be carriedout after the bleach-fixing process. As the processing solutions to beused in bleaching/fixing, use can be made of those usually used.

In some cases, it is preferable to carry out the stabilizing process, tostabilize silver salts and dye images, without carrying out thedesilvering process, after the development.

A combination of the color-developing agent of the present invention anda coupler with a known dye-providing compound, such as a dye developingagent or a compound capable of releasing a diffusible dye by redoxreaction explained later, may be used in the same photographicalelement. For example, it is possible to use a method in which an imagein yellow and an image in cyan can be formed by the color-developingagent of the present invention and a coupler and an image in magenta canbe formed by another dye image-forming compound.

An example of the dye image-forming compound that may besimultaneously-used in the present invention is a combination of a knowndeveloping agent with a coupler capable of reacting with this agent. Themanner of using this coupler is a manner in which an oxidized product ofthe developing agent, which is produced by redox reaction of a silversalt with the developing agent, reacts with the coupler, to form a dye,which manner is described in many literatures. This coupler may be afour-equivalent coupler or a two-equivalent coupler. Preferred is also atwo-equivalnt coupler which has a nondiffusible group as a split-offgroup and generates a diffusible dye by reaction with the oxidizedproduct of the developing agent. Specific examples of the developingagent and the coupler are described in detail, for example, in “TheTheory of the Photographic Process” (4th edition, by T. H. James,Macmillian, 1977), on pages 291-334 and pages 354-361, and inJP-A-58-123533, JP-A-58-149046, JP-A-58-149047, JP-A-59-111148,JP-A-59-124399, JPA-59-174835, JP-A-59-231539, JP-A-59-231540,JP-A-60-2950, JP-A-60-2951, JP-A-60-14242, JP-A-60-23474, andJP-A-60-66249.

In addition, as dye-image-forming compounds, for example, dye silvercompounds formed by combining an organosilver salt with a dye can bementioned. Specific examples of the dye silver compound are describedin, for example, Research Disclosure, May, 1978, pages 54 to 58(RD-16966):

Further, azo dyes used in the heat-developable silver dye bleach processcan be mentioned as another example of the dye-image-forming compound.Specific examples of azo dyes and bleaching methods are described in,for example, U.S. Pat. No. 4,235,957 and Research Disclosure, April,1976, pages 30 to 32 (RD-14433). In addition, leuco dyes described in,for example, U.S. Pat. Nos. 3,985,565 and 4,022,617 can be mentioned asanother example of the dye-providing substance. As the azo dye, the azodye represented by the formula (2-1) itself and the dye-forming compoundrepresented by the formula (2-5) of the second embodiment of the presentinvention can be also preferably used.

Further, as another example of the dye-image forming compound, compoundshaving a function of releasing or diffusing a diffusion dye imagewisecan be mentioned.

The compounds of this type can be represented by the following formula(LI):(Dye¹-X²)_(n)—Y¹  (LI)

Wherein Dye¹ represents a group to give a known dye, a group to give adye whose wavelength is temporarily shortened, or a group to give a dyeprecursor; X² represents a single bond or a linking group; Y¹ representsa group which has such a property that produces a difference indiffusibility of the compound represented by (Dye¹-X²)_(n)—Y¹correspondingly or inversely-correspondingly to the light-sensitivesilver salt having a latent image imagewise, or that releases Dye¹, toproduce a difference in diffusibility between Dye¹ released and(Dye¹-X²)_(n)—Y¹; n is 1 or 2, and when n is 2, two Dye¹-X²'s may be thesame or different.

As specific examples of the dye-providing substance represented by theformula (LI), dye developers in which a hydroquinon-series developer iscombined with a dye component, are described in U.S. Pat. Nos.3,134,764, 3,362,819, 3,597,200, 3,544,545 and 3,482,972. Also,substances releasing a diffusible dye by an intermolecular nucleophilicsubstitution reaction are described in JP-A-51-63618, and substancesreleasing a diffusible dye by an intermolecular rollback reaction ofisoxazolone ring are described in JP-A-49-111628. In all of thesemethods, a diffusible dye is released or diffused in undevelopedportions, but neither released nor diffused in developed portions.

A further method has been proposed, in which a dye-releasing compound ismade to be an oxidized product type incapable of releasing a dye and tocoexist together with a reducing agent or its precursor, and after beingsubjected to development, the dye-releasing compound is educed by-thereducing agent left non-oxidized, to thereby release a diffusible dye.Specific examples of the dye image-forming compound used in this methodare described in JP-A-53-110,827, JP-A-54-130,927, JP-A-56-164,342 andJP-A-53-35,533.

As substances releasing a dye in developed portions, substancesreleasing a diffusible dye by a reaction between a coupler having adiffusible dye in a split-off group and an oxidized product of adeveloping agent, are described in U.K. Patent No. 1,330,524,JP-B-48-39,165 and U.S. Pat. No., 3,443,940.

In the system using these color-developing agents, image contaminationwith oxidation-decomposed products of the developing agent causes aserious problem. A dye-releasing compound which needs no developingagent and the compound itself has reducibility, has been proposed tosolve the problem. Typical examples of the dye-releasing compoundinclude dye image-forming compounds described in U.S. Pat. Nos.3,928,312, 4,053,312, 4,055,428 and 4,336,322, JP-A-59-65839,JP-A-59-69839, JP-A-51-104,343, Journal of Research & Disclosure No.17465, U.S. Pat. Nos. 3,725,062, 3,728,113 and 3,443,939,JP-A-58-116537, JP-A-57-179840 and U.S. Pat. No. 4,500,626.

To form an color image in the present invention, it is possible to use acompound which releases, when silver ions are reduced to silver atomsunder a high temperature condition, a diffusible dye corresponding tothis reaction, that is, dye-providing compound.

Examples of the dye-providing compound include compounds having afunction of releasing a diffusible dye imagewise. Compounds of this typecan be represented by the following formula (LI-1):((Dye²)m-Y²)n¹-Z³¹  (LI-1)

wherein Dye² represents a group to give a dye or a dye precursor, or agroup to give a dye whose absorption region is temporarily changed to ashort wave or a precursor thereof; Y² represents a single bond or aconnecting group; Z³¹ represents a group which has a nature ofgenerating a difference in diffusibility of the compound represented bythe ((Dye²)m-Y²)n¹-Z³¹ in correspondence to a light-sensitive silversalt having a latent image imagewise, or a nature of releasing(Dye²)m-Y² and generating a difference in diffusibility between released(Dye²)m-Y² and the ((Dye²)m-Y²)n¹-Z³¹; m is an integer of 1-5, n¹ is 1or 2, and when either of m or n¹ is not 1, Dye²'s may be the same ordifferent. More specifically, the compounds of this type are thefollowing compounds {circle around (1)} and {circle around (2)}.

-   {circle around (1)} A compound which exhibits non-diffusibility by    itself and which-is a coupler having a diffusible dye as a split-off    group and releasing the diffusible dye by reaction with an oxidized    product of a reducing agent (DDR coupler). Specific examples thereof    are described in, for example, G.B. Patent No. 1,330,524,    JP-B-48-39165, U.S. Pat. Nos. 3,443,940, 4,474,867 and 4,483,914.-   {circle around (2)} A compound which exhibits non-diffusibility by    itself and which has ability to reduce-a silver halide or an    organosilver salt and releases a diffusible dye at the time of    reducing the opponent (DRR compound). Typical examples thereof are    described in U.S. Pat. Nos. 3,928,312, 4,053,312, 4,055,428 and    4,336,322, JP-A-56-65839, JP-A-59-69839, JP-A-53-3819 and    JP-A-51-104343, RD No. 17,465, U.S. Pat. Nos. 3,725,062, 3,728,113    and 3,443,939, JP-A-58-116537 and JP-A-57-179840, and U.S. Pat. No.    4,500,626. Specific examples of the DRR compound include compounds    described in the above-mentioned U.S. Pat. No. 4,500,626, col.    22-44. Compounds (1)-(3), (10)-(13), (16)-(19), (28)-(30),    (33)-(35), (38)-(40) and (42)-(64) in this U.S. Patent are    particularly preferred. Compounds described in U.S. Pat. No.    4,639,408, col. 37-39 are also useful. As dye-providing compounds    other than the above-mentioned couplers and the compounds of the    formula (LI-1), the following may be used: dye silver compounds    wherein an organosilver salt is combined with a dye (e.g. Research    Disclosure, May 1978, pages 54-58), azo dyes used in    heat-development silver dye bleach process (e.g. U.S. Pat. No.    4,235,957, Research Disclosure, April 1976, pages 30-32), and leuco    dyes (e.g. U.S. Pat. Nos. 3,985,565, 4,022,617).

As other dye-forming methods applicable to the present invention, thereare known methods of producing a diffusible dye by coupling reaction ofan incorporated-type developing agent with a coupler, as described inJP-A-8-286340, JP-A-10-142764 and JP-A-10-254111. In the presentinvention, it is particularly preferred to use a dye-forming method bysuch a coupling, or to use a dye-forming method by a DRR compound. Asthe incorporated-type developing agent, the color-developing agentrepresented by the formula (1-1) of the first embodiment of the presentinvention can also be preferably used.

The color diffusion transfer method is described hereafter.

In the system forming an image by diffusion transfer of a dye by usingthe light-sensitive material of the present invention, thelight-sensitive materials are. generally divided into two types: onemode in which a light-sensitive element and an image-receiving element(dye-fixing element) are formed separately by application on twosupports (these may be referred to a light-sensitive material anddye-fixing material, respectively), and the other mode in which both ofthe elements are formed by application on the same support.

The mutual relations of the light-sensitive element to the dye-fixingelement, to the supports and to a white reflecting layer, which aredescribed in the specification of JP-A-61-147244, pp58-59 and U.S. Pat.No. 4,500,626, 57th column, may be applied to the light-sensitivematerial of the present invention.

A typical mode of film unit in which a light-sensitive element and animage receiving element are formed on the same support, is one in whichthe image-receiving element and the light-sensitive element arelaminated on one transparent support and which eliminates the necessityof peeling the light-sensitive element from the image-receiving elementafter a transferred image is completed. To state in more detail, theimage-receiving element comprises at least one mordant layer (alsocalled to as an image-receiving layer or a dye-fixing layer). Also, thelight-sensitive element, in preferred embodiments, comprises acombination of a blue-sensitive emulsion layer, a green-sensitiveemulsion layer and a red-sensitive emulsion layer, a combination of agreen-sensitive emulsion layer, a red-sensitive emulsion layer and aninfrared-light-sensitive-emulsion layer, or a combination of ablue-sensitive emulsion layer, a red-sensitive emulsion layer and aninfrared-light-sensitive emulsion layer. Moreover, a yellow dyeimage-forming compound (a dye image-forming compound containing thecolor-developing agent of the present invention and a coupler; alsoreferred to as a dye-providing substance), a magenta dye image-formingcompound (a dye image-forming compound containing the color-developingagent of the present invention and a coupler), and a cyan dyeimage-forming compound (a dye image-forming compound containing thecolor-developing agent of the present invention and a coupler) arerespectively combined with the above emulsion layers. Thus, the abovemode of image-forming system according to the present invention isstructured. (Here, the “infrared-light-sensitive emulsion layer” meansan emulsion layer possessing sensitivity to light of 700 nm or more andespecially 740 nm or more). Each of these light-sensitive emulsionlayers may be divided into two or more layers as required. In addition,a white reflecting layer containing a solid dye, e.g., titanium oxide,may be formed between the mordant layer and the light-sensitive layer orthe layer containing the dye image-forming compound (the dyeimage-forming compound containing the color-developing agent of thepresent invention and a coupler), so as to appreciate the transferredimage through the transparent support.

A shading layer may be further provided between the white reflectinglayer and the light-sensitive layer so as to allow developmentprocessing completed under light. Also, as desired, a peelable layer maybe formed at a proper position to peel all or a part of thelight-sensitive element from the image-receiving element (embodimentslike this are described, for example, in JP-A-56-67840 and CanadianPatent No. 674,082).

Another form of a lamination type which requires peeling, is a colordiffusion transfer photographic film unit disclosed in JP-A-63-226649.That is, the color diffusion transfer photographic film unit comprises:a light-sensitive element having (a) a layer having a neutralizingfunction, (b) a dye receiving layer, (c) an peeling layer, and (d) atleast one silver halide emulsion layer combined with a dye image formingsubstance, successively, in this order, on a white support; an alkalineprocessing composition containing a light-shielding agent; and atransparent cover sheet, and further comprises a layer havinglight-shielding function on the side opposite to the side of theemulsion layer on which the processing composition is applied(expanded).

In another mode which does not need peeling, the light-sensitive elementis formed by application on one transparent support, a white reflectinglayer is formed by application on the light-sensitive element, and animage-receiving layer is further laminated on the white reflectinglayer. The mode in which an image-receiving element, a white reflectinglayer, a peelable layer and a light-sensitive element are laminated onthe same support, and the light-sensitive element is intentionallypeeled from the image-receiving element, is described in U.S. Pat. No.3,730,718.

On the other hand, the typical modes in which the light-sensitiveelement and the image-receiving element are separately formed byapplication on two supports are generally divided into two categories:one is a peelable type and the other is a peeling-needless type. Tomention these types in detail, in a preferred embodiment of the peelablefilm unit, a light-reflecting layer is provided on the back-surface of asupport and at least one image-receiving layer is formed by applicationon the surface of the support. Also, the light-sensitive element isformed by application on a support provided with a shading layer. Thisembodiment is devised such that the surface of the side applied thelight-sensitive layer does not face the surface of the side applied themordant layer until the exposure is finished, but the surface of theside applied the light-sensitive layer is overturned so that it facesand overlaps the surface of the side applied the mordant layer after theexposure was finished (for example, during development processing). Thelight-sensitive element is peeled from the image-receiving elementimmediately after the transferred image is completed in the mordantlayer.

In a preferred embodiment of the peeling-needless film unit, at leastone mordant layer is formed on a transparent support, and alight-sensitive element is formed by application on a supporttransparent or provided with a shading layer, and the surface of theside applied the light-sensitive layer and the surface of the sideapplied the mordant layer are facing and are overlapped on each other.

The aforementioned modes may be applied to both of a system ofdevelopment using an alkaline processing solution which is developed(expanded) on a light-sensitive material, and a heat development system.Particularly, in the former system, a container (processing ortreating-element) which contains the alkaline processing solution andcan be burst by pressure, may be combined. Among these systems, in thepeeling-needless film unit in which an image-receiving element and alight-sensitive element are laminated on one support, the processingelement is preferably disposed between the light-sensitive element and acover sheet which is overlapped on the light-sensitive element. Also, inthe mode in which a light-sensitive element and an image-receivingelement are separately formed by application on two supports, theprocessing element is preferably disposed between the light-sensitiveelement and the image-receiving element during the developing time atthe latest. Preferably the processing element contains a shading agent(e.g., carbon black and dyes which are changed in color depending uponpH) and/or a white pigment (e.g. titanium oxide) according to the modeof film unit. In a film unit of the type which carries out developmentusing the alkaline processing solution, preferably aneutralization-timing mechanism composed of a combination of aneutralization layer and a neutralization timing layer is incorporatedinto the cover sheet, the image-receiving element or the light-sensitiveelement.

As the mordant used in the aforementioned image-receiving element or thedye-fixing element explained later, a polymer mordant is preferable.Here, the polymer mordant includes, for example, polymers containing atertiary amino group, polymers containing a nitrogen-containingheterocyclic moiety, and polymers containing a quaternary cationicgroup.

Specific examples of these polymer mordants are described inJP-A-61-147244, pp98-100 and U.S. Pat. No. 4,500,626, 57th-60th columns.

The following will describe the image-receiving element for the colordiffusion transfer method in more detail. This image-receiving elementin color diffusion transfer method preferably comprises at least onelayer containing a mordant (a mordanting layer). As the mordant, any oneof mordants known in the field of photography may be used. Specificexamples thereof are described in G.B. Patents No. 2,011,912, No.2,056,101 and 2,093,041, U.S. Pat. Nos. 4,115,124, 4,273,853 and4,282,305, JP-A-59-232340, JP-A-60-118834, JP-A-60-128443,JP-A-60-122940, JP-A-60-122921 and JP-A-60-235134.

Various other additives may be appropriately used in the image-receivingelement for the color diffusion transfer method. These will be describedin the item of a dye fixation element (image-receiving element) for thecolor diffusion transfer method for heat-development.

The following will describe light-sensitive elements for the colordiffusion transfer method. The contents described in the right lowercolumn, line 8 on page (17) of JP-A-2-32335 to the right lower column,line 19 on page (20) thereof can be applied to a silver halide emulsion,a spectral sensitizing dye, an emulsion layer, a multilayer structuresfor full colors, a processing composition, a film unit for the colordiffusion transfer method, and its constituting layers, which are usedin the color diffusion transfer method.

The light-sensitive element used in the present invention may comprise,as required, various additives which are known as materials used in aheat-developable light-sensitive element, and layers other than thelight-sensitive layer, such as a protective layer, intermediate layer,antistatic layer, antihalation layer, peelable layer which makes peelingfrom a dye-fixing element easy, and a matted layer. These variousadditives include plasticizers, matt agents, sharpness-improving dyes,antihalation dyes, surfactants, fluorescent brighteners, antislipagents, antioxidizing agents, anti-fading agents, and diffusibledye-trapping agent, which are described in Journal of Research &Disclosure, the June issue, pp9-15 (1978) and JP-A-61-88256.

Especially the protective layer is generally made to contain organic orinorganic matt agents to prevent adhesion. This protective layer mayalso include a mordant and a UV-ray absorber. The protective layer andthe intermediate layer may be respectively structured of two or morelayers.

Also, the intermediate layer may include a reducing agent, a UV-rayabsorber and a white pigment, e.g., titanium dioxide, to preventcolor-fading and color mixing. The white pigment may be added not onlyto the intermediate layer but also to the emulsion layer, to improve thesensitivity.

The dye-fixing element may be provided with an auxiliary layer(s), suchas a protective layer, peelable layer and curling-preventive layer, asrequired. Particularly it is useful to provide the protective layer. Oneor more of the aforementioned layers may include hydrophilic heatsolvents, plasticizers, anti-fading agents, UV-ray absorbers, anti-slipagents, matt agents, antioxidizing agents, dispersed vinyl compounds forincreasing dimentional stability, surfactants, luminescent whiteners,and the like. Further, particularly, in the system wherein heatdevelopment and diffusion transfer of a dye are carried outsimultaneously in the presence of a small amount of water, a base and/orbase precursor, which is described later, is preferably contained in thedye-fixing element, with a viewpoint of increasing the preservability ofthe light-sensitive element. Specific examples of these additives aredescribed in JP-A-61-88256, pages 101 to 120.

A peeling layer for the color diffusion transfer method will bedescribed. The peeling layer used in the present invention can beprovided on an arbitrary position of a light-sensitive sheet inside theunit after processing. Examples of the material of the peeling layerthat can be used include those described in for example, JP-A-47-8237,JP-A-59-220727, JP-A-49-4653, JP-A-49-4334, JP-A-50-65133 andJP-A-45-24075, U.S. Pat. Nos. 3,220,835, 4,359,518, 3,227,550,2,759,825, 4,401,746 and 4,366,227. Specifically, a water-soluble (oralkali-soluble) cellulose derivative may be used. Examples thereofinclude hydroxyethylcellulose, cellulose acetate phthalate, elasticizedmethylcellulose, ethylcellulose, cellulose nitride, andcarboxymethylcellulose. The following may be used: various naturalpolymers, such as alginic acid, pectin and Arabian gum; various modifiedgelatins, such as acetylated gelatin and phthalated gelatin; polyvinylalcohol; polyacrylate; polymethyl methacrylate; and copolymers thereof.Among these compounds, a cellulose derivative is preferred andhydroxyethylcellulose is particularly preferred as the material forpeeling.

Besides the water-soluble cellulose derivative, a particulate substanceof an organic polymer or the like may be used as the material forpeeling. Examples of the organic polymer which can be used in thepresent invention include polymer latexes made, for example, ofpolyethylene, polystyrene, polymethyl methacrylate, polyvinylpyrrolidone and-butyl acrylate, each of which has an average particlesize of 0.01-10 μm. It is preferred to use a light-reflective hollowpolymer latex composed of a material whose inside contains air and whoseoutside is made of an organic polymer, as will be described below. Thislight-reflective hollow polymer latex may be synthesized by the methoddescribed in JP-A-61-151646.

In the light-sensitive element and/or the dye-fixing element accordingto the present invention, an image-forming accelerator may be used. Theimage-forming accelerate has an ability to accelerate a redox reactionbetween a silver salt oxidizing agent and a reducing agent, anability-to accelerate reactions to form a dye from the dye image-formingcompound (dye-providing substance) containing the coupler and thecolor-developing agent of the present invention, to decompose the dye orto release a diffusible dye, and an ability to accelerate the transferof the dye from the structural layer of the light-sensitive element tothe dye-fixing layer. From the physicochemical abilities, theimage-forming accelerators are classified into bases or base precursors,nucleophilic compounds, high boiling point organic solvents (oils), heatsolvents, surfactants, compounds which interact with silver or silverions, and the like. It is to be noted that these material groups usuallyhave duplex abilities and possess some of the above accelerating effectsin general. The details of these materials are described inJP-A-61-93451, pp67-71.

There are various methods for the production of a base. Compounds usedin these methods are all useful as a base precursor.

The base precursor is, for example, a salt of a base and an organic acidwhich is decarboxylated by heat, or a compound which releases an amineby intermolecular nucleophile substitution reaction, Lossenrearrangement or Beckman rearrangement. Specific examples thereof aredescribed in U.S. Pat. Nos. 4,514,493 4,657,848, and the like.

In the system for performing heat development and transfer of a dyesimultaneously-in the presence of a small amount of water, the method ofincorporating the base and/or the base precursor into the dye fixationmaterial is preferred for making the stability of the heat-developablelight-sensitive material high.

In addition to the above, there are, for example, a method described inE.P. Patent No. 0210660A2 and U.S. Pat. No. 4,740,445, in which a baseis generated by mixing a metal compound (e.g., a metal salt), which issparingly soluble in water, with a compound (a complex-forming compoundor complexing agent) which can react with the metal ion constituting themetal compound, which is sparingly soluble in water, to form a complex;and a method described in JP-A-61-232451 in which a base is generated byelectrolysis. Especially, the former method is effective.

Given as examples of the-metal compound which is sparingly soluble inwater include carbonates, hydroxides or oxides of zinc, aluminum,calcium or barium. The complex-forming compounds are explained indetail, for example, in “Critical Stability Constants” written jointlyby “A. E. Martell, R. M. Smith, Vol No. 4 and Vol. No. 5, Plenum Press.Specific examples include salts of aminocarboxylic acids, iminodiaceticacids, pyridinecarboxylic acids, aminophosphoric acids, carboxylic acids(mono-, di-, tri-, tetra-carboxylic acids and compounds having any ofsubstituents, e.g., a phosphono, hydroxy, oxo, ester, amide, alkoxy,mercapto, alkylthio or phosphino group), hydroxam acids, polyacrylatesor polyphosphoric acids and alkali metals, guanidines, amidines orquaternary ammonium salts.

It is advantageous to add these metal compound which is sparing solublein water and complex-forming compound to each of the light-sensitiveelement and dye-fixing element.

In the light-sensitive element and/or the dye-fixing element for use inthe present invention, in order to obtain a constant image all the time,against fluctuation of the processing temperature and the processingtime at the time of development, various development-stopping agents canbe used.

Herein, the term “a development-stopping agent” means a compound thatneutralizes bases quickly or reacts quickly with bases after properdevelopment, to lower the base concentration in the film, to stop thedevelopment; or a compound that interacts with silver and silver salts,to inhibit the development. Specific examples include acid precursorsthat release an acid when heated, electrophilic compounds that undergo asubstitution reaction with coexisting bases when heated,nitrogen-containing heterocyclic compounds, mercapto compounds, andtheir precursors (for example, compounds described in JP-A-60-108837,JP-A-60-192939, JP-A-60-230133, JP-A-60-230134, and JP-A-62-253159,pages (31)-(32)).

Also, compounds which release a mercapto compound by heating are alsouseful. These compounds are described in, for example, JP-A-61-67851,JP-A-61-147244, JP-A-61-124941, JP-A-61-185743, JP-A-61-182039,JP-A-61-185744, JP-A-61-184539, JP-A-61-188540 and JP-A-61-53632.

As the binder of light-sensitive element and/or dye-fixing element ofthe present invention, a hydrophilic binder can be used. Typically, thehydrophilic binder is a transparent or semitransparent hydrophilicbinder. Specifically, examples include natural compounds such asproteins including gelatin, gelatin derivatives and the like, orpolysaccharides including cellulose derivatives, starches, gum-arabic,dextrans, and the like; and synthetic polymer compounds such as watersoluble polyvinyl compounds including polyvinyl pyrrolidones, andacrylamide polymers. A disperse vinyl compound which is used in the formof a latex and increase the dimentional stability of photographicmaterials may also be used. These binders may be used either singly orin combinations.

It is preferable that the amount of the binder to be applied in thepresent invention is 20 g or less, more preferably 10 g or less andfurther preferably 7 g or less per 1 m².

A ratio of a high-boiling point organic solvent, which is dispersed inthe binder together with hydrophobic compounds such as thecolor-developing agent of the present invention and the coupler, to thebinder is as follows: the amount of the solvent is generally 1 ml orless, preferably 0.5 ml or less and more preferably 0.3 ml or less, perg of the binder.

The structural layer (e.g., a photographic emulsion layer and adye-fixing layer) of the dye-fixing element and/or the light-sensitiveelement of the present invention may contain an inorganic, or organichardener.

Specific examples of the hardener include those described in thespecification of JP-A-61-147244, pp94-95 and in the specification ofJP-A-59-157636, pp38. These compounds may be used either singly or incombination.

To accelerate the dye transfer, a hydrophilic heat solvent that is solidat normal temperatures and melts at a higher temperature can be built inthe light-sensitive element and/or the dye-fixing element. Thehydrophilic heat solvent can be built in any of the light-sensitiveelement and the dye-fixing element, and it may be built in bothelements. Further, the layer wherein the hydrophilic heat solvent isbuilt in may be any of the light-sensitive silver halide emulsion layer,the intermediate layer, the protective layer, and the dye-fixing layer,but preferably it is built-in the dye-fixing layer and/or the layeradjacent thereto. Examples of the hydrophilic heat solvent includeureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, andother heterocyclic compounds. Further, to accelerate the dye transfer,high-boiling organic solvent can be contained in a light-sensitiveelement and/or dye-fixing element.

The support to be used in the light-sensitive element and/or thedye-fixing element of the present invention can stand against treatingtemperature. As a usual support, glasses, papers, polymer films, metalsor similar materials may be used and also those described as supports inthe specification of JP-A-61-147244, pp95-96 may be used.

The support is generally a support for photography, such as paperdescribed in “Basis of Photographic Engineering—Silver Salt PhotographyVersion—”, pages (223)-(224), edited by-the Society of PhotographicSociety and Technology of Japan, and published by Corona Publishing Co.,Ltd. (1979), or a synthetic polymer (film). Specific examples thereofinclude polyethylene terephthalate, polyethylene naphthalate,polycarbonate, polyvinyl chloride, polystyrene, polypropylene,polyimide, and cellulose (for example, triacetylcellulose) films, filmswherein a pigment such as titanium oxide is incorporated into any one ofthese films, synthetic paper made from polypropylene, mixed paper madefrom synthetic resin pulp such as polyethylene and natural pulp, Yankeepaper, baryta paper, coated paper (particularly, cast-coated paper),metal, cloth, and glass.

These supports may be used alone, or may be used as a support whereinone surface or two surfaces of any one of these supports is laminatedwith synthetic polymer such as polyethylene. If necessary, a pigment ora dye such as titanium oxide, ultramarine blue or carbon black may beincorporated into the laminating layer.

Besides, it is possible to use supports described in JP-A-62-253159,pages (29)-(31), JP-A-1-161236, pages (14)-(17), JP-A-63-316848,JP-A-2-22651 and JP-A-3-56955, U.S. Pat. No. 5,001,033, and the like.

An antistatic agent including carbon black, a hydrophilic binder and asemi-conductive metal oxide such as alumina sol or tin oxide may beapplied to the back surface of the above-mentioned support.Specifically, supports described in JP-A-63-220246 and the like may beused.

In order to improve adhesiveness between the surface of the support andthe hydrophilic binder, it is preferred to subject the surface tovarious surface treatments or undercoating.

The light-sensitive material and/or the dye fixation material of thepresent invention may be in the form having an electrically conductiveheating layer as heating means for heat development anddye-diffusion/transfer. As the heating element in this case, a heatingelement described in JP-A-61-145544 may be used.

A transparent or opaque exothermic element in this case may be made as aresistive exothermic body by making use of conventionally knowntechniques. As the method of producing the resistive exothermic body,there are a method which makes use of a thin film of an inorganicmaterial exhibiting semiconductivity and a method which makes use of anorganic thin film in which electroconductive fine grains are dispersedin a binder. As materials used in these methods, compounds described inthe specification of JP-A-61-29835 may be used.

In the system for forming an image by diffusion transfer of a dye,various compounds may be added to layers constituting theheat-developable light-sensitive material of the present invention, inorder to fix unnecessary dyes or colorants or make them colorless toimprove the white background of resultant images.

Specifically, it is possible to use compounds described in EP-A-353,741and EP-A-461,416, and JP-A-63-163345 and JP-A-62-203158.

Various pigments or dyes may be used in layers constituting theheat-developable light-sensitive material of the present invention toimprove color differentiation property and sensitization.

Specifically, it is possible to use compounds described in theabove-mentioned Research Disclosure or compounds and layer-structuresdescribed in EP-A-479,167 and EP-A-502,508, JP-A-1-167838,JP-A-4-343355, JP-A-2-168252 and JP-A-61-20943, and EP-A-479,167 andEP-A-502,508.

In the system for forming an image by diffusion transfer of a dye, a dyefixation material is used together with the heat-developablelight-sensitive material. The dye fixation material may be in the formin which it is applied to a support different from a support to whichthe light-sensitive material is applied, or may be in the form in whichit is applied to the same support to which the light-sensitive materialis applied. With respect to the mutual relationship between thelight-sensitive material and the dye fixation-material, the relationshipto the support, and the relationship to a white reflection layer,relationships described in U.S. Pat. No. 4,500,626, col. 57 can beapplied to the present invention.

The dye fixation material which is preferably used in the presentinvention has at least one layer comprising a mordant and a binder. Asthe mordant, a mordant known in the photographic field can be used.Specific examples thereof include those described in U.S. Pat. No.4,500,626, col. 58-59, JP-A-88256, pages (32)-(41), JP-A-1-161236, pages(4)-(7), and U.S. Pat. Nos. 4,774,162, 4,619,883 and 4,594,308. A dyeacceptable polymer compound as described in U.S. Pat. No. 4,463,079 maybe used.

The binder which is used in the dye fixation material of the presentinvention is preferably the above-mentioned hydrophilic binder. It ispreferred to use this binder together with any one of carraghenane asdescribed in EP-A-443,529 and latexes having a glass-transitiontemperature of 40° C. or less as described in JP-B-3-74820.

If necessary, auxiliary layers such as a protective layer, a peelinglayer, an undercoat layer, an intermediate layer, a backing layer and acurl-inhibiting layer may be formed in the dye fixation material. Theformation of the protective layer is particularly useful.

In layers constituting the heat-developable light-sensitive material andthe dye fixation material, a plasticizer, a lubricant or a high boilingpoint organic solvent as an improver of capability of peeling of thelight-sensitive material from the dye fixation material may be used.Specific examples thereof are described in the above-mentioned ResearchDisclosures, JP-A-62-245253, and the like.

For the above-mentioned purposes, various silicone oils (all siliconeoils including dimethylsilicone oil and modified silicone oils in whichvarious organic groups are introduced into dimethylsiloxane) may beused. Useful examples thereof include various modified silicone oilsdescribed in a technical material “Modified Silicone Oils” pages 6-18B,published by Shin-Etsu Chemical-Co., Ltd. Carboxy-modified silicone(trade name: X-22-3710) and the like are particularly useful.

Silicone oils described in JP-A-62-215953 and JP-A-63-46449 are alsouseful.

A fading inhibitor (anti-fading agent) may be used in theheat-developable light-sensitive material or the dye fixation material.Examples of the fading inhibitor are an antioxidant, an ultravioletabsorber, and some kinds of metal complexes. Dye image stabilizers,ultraviolet absorbers and the like described in the above mentionedResearch Disclosures are also useful.

Examples of the antioxidant include chroman compounds, coumaranecompounds, phenol compounds (for example, hindered phenols),hydroquinone derivatives, hindered amine derivatives, and spiroindanecompounds. Compounds described in JP-A-61-159644 are also useful.

Examples of the ultraviolet absorber include benzotriazole compounds(for example, U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (forexample, U.S. Pat. No. 3,352,681), benzophenone compounds (for example,JP-A-46-2784), and compounds described in, for example, JP-A-54-48535,JP-A-62-136641 and JP-A-61-88256. An ultraviolet absorbing polymerdescribed in JP-A-62-260152 is also useful.

Examples-of the metal complexes include compounds described in U.S. Pat.Nos. 4,241,155, 4,245,018, col. 3-36, and U.S. Pat. No. 4,254,195, col.3-8, JP-A-62-174741, JP-A-61-88256, pages (27)-(29), JP-A-63-199248,JP-A-1-75568 and JP-A-1-74272, and the like.

The fading inhibitor for preventing the color of the dye transferred tothe dye fixation material from fading out may be beforehand contained inthe dye fixation material, or it may be supplied from the outside, forexample, from the heat-developable light-sensitive material or atransferring solvent, which will be described alter, to the dye fixationmaterial.

Any combination of two or more selected from the antioxidants, theultraviolet absorbers and the metal complexes may be used.

A fluorescent bleaching agent may be used in the heat-developablelight-sensitive material or the dye fixation material. It isparticularly preferred to incorporate the fluorescent bleaching agentinto the dye fixation material or supply the agent from the outside, forexample, from the heat-developable material or the transferring solvent.Examples thereof include compounds described in “The Chemistry ofSynthetic Dyes”, Vol. 5, Chapter 8, edited by K. Veenkataraman, andJP-A-61-143752. Specific examples thereof include stylbene compounds,coumarin compounds, biphenyl compounds, benzoxazolyl compounds,naphthalimide compounds, pyrazoline compounds, and carbostyrylcompounds.

The fluorescent bleaching agent may be combined with the fadinginhibitor or the ultraviolet absorber and the combination may be used.Specific examples of the fading inhibitor, the ultraviolet absorber, andthe fluorescent bleaching agent are described in JP-A-62-215272, pages(125)-(137) and JP-A-1-161236, pages (17)-(43).

In the present invention, to apply a heat developing light-sensitivelayer, protective layer, intermediate layer, undercoat layer, backinglayer, dye-fixing layer and other layers, a method described in U.S.Pat. No. 4,500,626, 55th-56th columns can be used.

As a light source for image exposure used to record an image in thelight-sensitive element, radiation rays including visible light may beused. In general, light sources used in usual color printing, forexample, a tungsten lamp, mercury lamp, halogen lamps such as an iodinelamp, xenon lamp, laser light source, CRT light source or light emittingdiode (LED), which are all described in JP-A-61-147244, p100 and U.S.Pat. No. 4,500,626, 56th column, may be used.

In the image-forming method involving a heating step to which thepresent invention is applied, for example, a heat developing step and adye-transfer step are carried out either separately or simultaneously.Also, both steps may be successive in the meaning of the fact that atransfer operation is carried out in succession to a developingoperation in one step.

For example, there are (1) a method in which an image is formed on thelight-sensitive element by exposure, followed by heating, thereafter adye-fixing element is overlapped on the light-sensitive element and, asrequired, heated to transfer a movable dye to the dye-fixing element,and (2) a method in which an image is formed on the light-sensitiveelement by exposure and a dye-fixing element-is overlapped on thelight-sensitive element, followed by heating. The aforementioned methods(1) and (2) may be applied either in substantially the absence of wateror in the presence of minute water.

The development can be made at about 50° C. to about 250° C., but theheating temperature in the heat developing step is preferably 60° C. to180° C., more preferably 70° C. to 180° C. and particularly preferably75° C. to 150° C. In the case of heating in the presence of minutewater, the upper limit of the heating temperature is below the boilingtemperature. The step of diffusion transfer of a dye may be carried outsimultaneously with heat development, or it may be carried out after thecompletion of the heat-development step. When the transfer step isperformed after the heat developing step is finished, although thetransfer can be made in a temperature range between the temperature inthe heat developing step and room temperature, the heating temperaturein the transfer step is more preferably 50° C. or higher, but equal toor lower than the temperature that is lower by 10° C. than thetemperature in the heat developing step.

In a preferred image-forming method according to the present invention,an image is exposed or heating is performed in the presence of minutewater and a base and/or a base precursor when an image is exposed, and adiffusible dye generated in the portions corresponding or reverselycorresponding to a silver image at the same time of developing istransferred to the dye-fixing layer. This method ensures that theproduction and releasing reactions of the diffusible dye run veryquickly, and hence the diffusible dye is transferred to the dye-fixinglayer rapidly, thereby to obtain a high density color image in a shortperiod of time.

The amount of water to be used in this embodiment can be as small as 0.1times and preferably more than 0.1 times the weight of the total appliedfilm of the light-sensitive element and dye-fixing layer, and equal toor less than the weight (specifically, equal to or less than the amountcalculated by subtracting the weight of the total applied film from theweight of the solvent corresponding to the maximum swelled volume of thetotal applied film) of the solvent corresponding to the maximum swelledvolume of the total applied film.

The state of the film during swelling is unstable and local bleeding islikely caused depending upon the conditions. In order to evade thisphenomenon, the amount of water is preferably equal to or smaller thanthe amount corresponding to the volume of the total applied film of thelight-sensitive element and dye-fixing element when the film reaches amaximum swelling. Concretely, the amount of water is preferably in arange between 1 and 50 g, more preferably 2 and 35 g and furtherpreferably.3 and 25 g per total m² of the sum of the light-sensitiveelement and dye-fixing element.

A base and/or base precursor used in this embodiment may be incorporatedinto any of the light-sensitive element and the dye-fixing element. Thebase and/or base precursor may also be supplied after it is dissolved inwater.

In the above embodiment, it is preferable that the image-formingreaction system be made to contain a metal compound (e.g., a basic metalcompound which is sparingly soluble in water), which is sparinglysoluble in water, as a base precursor, and a compound (a complexingagent) that can react with the metal ion constituting the metalcompound, which is sparing soluble in water, by using water as a mediumto form a complex; and an alkali be generated by the reaction of thosetwo compounds during heating, to raise the pH of the system. Here, theimage reaction system means the region where an image-forming reactionis caused. Given as specific example of the region are layers belongingto both of the light-sensitive element and dye-fixing element. In thecase where two or more layers are present, the reaction system maybeincluded in any of these layers.

It is necessary to add the metal compound that is sparingly soluble inwater and the complex-forming compound to at least separate layers toprevent the both from reacting with each other by the time ofdevelopment processing. For example, in a so-called monosheet materialin which the light-sensitive element and the dye-fixing element areformed on the same support, it is preferable that both of the elementsare incorporated into layers separately, and that one or more layers areinterposed between these separate layers. In a more preferredembodiment, the metal compound that is sparingly soluble in water andthe complex-forming compound are respectively contained in each layerformed on separate supports. For example, it is preferable that themetal compound which is sparingly soluble in water be contained in thelight-sensitive element and the complex-forming compound be contained inthe dye-fixing element having a support different from that of thelight-sensitive element. The complex-forming compound may be suppliedafter it is dissolved in water allowed to coexist. Preferably the metalcompound which is sparingly soluble in water is contained in the form ofa fine grain dispersion prepared according to the methods described in,for example, JP-A-56-17480-and JP-A-53-102733. Preferably the averagegrain size of the fine grain dispersion is 50 μm or less andparticularly preferably 5 μm or less. The metal compound which issparingly soluble in water may be added to any one of thelight-sensitive layer, intermediate layer and protective layer of thelight-sensitive element and may be added separately to two or morelayers.

When the metal compound which is sparingly soluble in water or thecomplex-forming compound is to be contained in a layer on a support, theamount of the compound(s) to be added depends on the type of compound,the grain size of the metal compound which is insoluble in water and therate of reaction for forming a complex. The metal compound or thecomplex-forming compound is used preferably in an amount of 50% byweight or less, and~more preferably in an amount ranging from 0.01% byweight to 40% by weight, in term of weight of the coated film. When thecomplex-forming compound is supplied after it is dissolved in water, itsconcentration is in a range preferably from 0.005 mols to 5 mols andparticularly preferably from 0.05 mols to 2 mols, per 1 liter of thesolution. In the present invention, the content of the complex-formingcompound in the reaction system is preferably 1/100 times to 100 timesand particularly preferably 1/10 times to 20 times the content of thecompound, which is sparingly soluble in water, in terms of molar ratio.

A method of supplying water to the light-sensitive layer or thedye-fixing layer includes, for example, one described in JP-A-61-147244,from p101, line 9 to p102, line 4.

As heating means in the developing step and/or transfer step, there aremeans described in JP-A-61-147244, from p106, line 14 to p103, line 11,for example, a heating plate, iron and heat roller. A method may beadopted in which layers of conductive materials such as graphite, carbonblack and metals are overlapped on the light-sensitive element and/ordye-fixing element and current is allowed to flow through the conductivelayer to heat directly.

As pressure conditions and a method of applying pressure when thelight-sensitive element and the dye-fixing element are overlapped oneach other and stuck to each other, a method described inJP-A-61-147244, pp103 to 104 may be used.

To process the photographic elements for use in the present invention,any of various heat development apparatuses can be used. For example,apparatuses described, for example, in JP-A-59-75247, JP-A-59-177547,JP-A-59-181353, and JP-A-60-18951, unexamined published Japanese UtilityModel Application (JU-A) No. 62-25944can be preferably used.

The transfer of a dye is caused only-by heat. A solvent for acceleratingthe dye-transfer may be used. The solvent is described in U.S. Pat. Nos.4,704,345 and 4,740,445, JP-A-61-238056 and the like. A method ofcarrying out heating in the presence of a small amount of a solvent(particularly, water) and then performing development and transfersimultaneously or continuously is also useful. In this method, theheating temperature is preferably from 50° C. to the boiling point ofthe solvent. When the solvent is, for example, water, the heatingtemperature is preferably 50-100° C.

Examples of the solvent used to accelerate development and/or diffuseand transfer a dye include water, aqueous basic solutions containing aninorganic alkali metal salt or an organic base (materials described inthe item of the image-forming accelerator can be used as the base), lowboiling point solvents, and mixed solutions of a low boiling solvent andwater or the abovementioned aqueous basic solution. It is possible toincorporate a surfactant, an antifoggant, a compound which is combinedwith a slightly soluble metal salt to form a complex, an antifungalagent, or an anti-bacterial agent, into the solvent.

The solvent used in the steps of heat development and diffusion/transferis preferably water. The water may be any water which is generally used.Specific examples thereof include distilled water, city water, wellwater and mineral water. In a heat developing apparatus in which theheat-developable light-sensitive material and the dye fixation materialof the present invention are used, water may be used in a batch form orcirculating form. In the latter case, water containing components elutedfrom the material is used. Apparatuses and water described inJP-A-63-144354, JP-A-63-144355, JP-A-62-38460 and JP-A-3-210555 may beused.

The above-mentioned solvent may be supplied to the heat-developablelight-sensitive material, the dye fixation material, or both of the two.The amount to be used thereof is equal to or less than the mass of thesolvent corresponding to the maximum swelling volume of all of theapplied films.

As the method of supplying water, for example, the method described inJP-A-62-253159, page (5) and JP-A-63-85544 is preferably used. Thesolvent may be confined in microcapsules, or may be beforehandincorporated, in the form of hydrate, into the heat-developablelight-sensitive material, the dye fixation material, or both of the two.

The temperature of the supplied water may be 30-60° C. as described inthe above-mentioned JP-A-63-85544. Particularly in order to preventpropagation of unwanted bacteria in water, it is useful to set thetemperature to 45° C. or higher.

The dye of the present invention when used as an azo dye itself, may beused in ink-jet recording system.

The ink-jet recording system can be classified to a manner using oilyink, a manner using aqueous ink and a manner using solid ink (at roomtemperature). These manners are specifically described in JP-A-3-239175,JP-A-7-118584, and JP-A-7-70490.

The dye of the present invention is also useful as athermally-transferring dye.

A thermally-transferring dye releasing material using thethermally-transferring dye may be used in the form of a sheet, acontinuous roll or a ribbon. The dye of the present invention can beapplied to the methods described in JP-B-4-15760 and JP-A-1-188391 andJP-A-3-83685.

By using the color-developing agent of the present invention, good colorforming property can be obtained in a short time, and further a colordeveloped image excellent in stability against light, heat, humidity andthe like can be obtained.

According to the silver halide photographic light-sensitive material andimage-forming method using the novel color-developing agent of thepresent invention, good developed color can be obtained at the time ofdevelopment, and an image excellent in image quality and image-stabilitycan be formed.

According to the azo dye and silver halide color photographiclight-sensitive material of the present invention, an image having agood hue and a high developed color density can be obtained, and furtherstability thereof against light, heat, air, chemicals and the like isimproved.

The azo dye of the present invention is preferable as a yellow dye or amagenta dye, it exhibits excellent absorption characteristics, and it isimproved in stability against light, humidity, heat, air, chemicals andthe like. The silver halide photographic light-sensitive material of thepresent invention that contains a dye-image-forming compound preferableas a yellow or magenta dye-image-forming compound, exhibits excellentabsorption characteristics, and it is improved in stability againstlight, humidity, heat, air, chemicals and the like. The silver halidephotographic light-sensitive material of the present invention thatcontains the azo dye, exhibits excellent absorption characteristics, andit is improved in stability against light, humidity, heat, air,chemicals and the like.

The present invention is described in more detail with reference to thefollowing examples, but the present invention is not limited thereto.

EXAMPLES Example 1-1

A dye fixation material R101 was formed by the following method.

On a surface of a support (thickness: 152 μm), the core material ofwhich was made of pulp, a surface PE layer (thickness: 36.0 μm) and asurface undercoat layer (thickness: 0.1 μm) were successively formed inthis order from the side of the support. On the back surface thereof, aback PE layer (thickness: 27.0 μm) and a back undercoat layer(thickness: 0.5 μm) were successively formed in this order from the sideof the support. Components of the respective layers are shown in Table1.

TABLE 1 Constitution of Support Film Name of layer Composition thickness(μm) Surface Gelatin 0.1 undercoat layer Surface PE layer Low-densitypolyethylene (Density 36.0 (Glossy) 0.923): 90.2 parts Surface-processedtitanium oxide: 9.8 parts Ultramarine: 0.001 parts Pulp layer Finequality paper (LBPK/NBSP = 152 6/4, Density 1.053) Back-surface PEHigh-density polyethylene 27 layer (Matt) (Density 0.955) Back-surfaceStyrene/acrylate copolymer 0.1 undercoat layer Colloidal silicaPolystyrenesulfonic acid sodium salt 215.2

Then, coating solutions for forming six (6) layers were applied bymultilayer coating to the surface of the surface undercoat layer to formthe six layers on the support. Thus, the dye fixation material R101 wasformed. Constituting components of the respective layers are shown inTables 2 and 3.

TABLE 2 Constitution of dye-fixing material R101 Coated amount Number oflayer Additive (mg/m²) Sixth layer Water-soluble polymer (1) 130Water-soluble polymer (2) 35 Water-soluble polymer (3) 45 Potassiumnitrate 20 Anionic surfactant (1) 6 Anionic surfactant (2) 6 Amphotericsurfactant (1) 50 Stain-preventing agent (1) 7 Stain-preventing agent(2) 12 Matting agent (1) 7 Fifth layer Gelatin 250 Water-soluble polymer(1) 25 Anionic surfactant (3) 9 Hardener (1) 185 Forth layer Mordant (2)1850 Water-soluble polymer (2) 260 Water-soluble polymer (4) 1400Dispersion of latex (1) 600 Anionic surfactant (3) 25 Nonionicsurfactant (1) 18 Citric acid 15 Guanidine picolinate 2550 Sodiumquinolinate 350 Third layer Gelatin 370 Mordant (1) 300 Anionicsurfactant (3) 12

TABLE 3 Coated amount Number of layer Additive (mg/m²) Second layerGelatin 700 Mordant (1) 290 Water-soluble polymer (1) 55 Water-solublepolymer (2) 330 Anionic surfactant (3) 30 Anionic surfactant (4) 7High-boiling organic solvent (1) 700 Brightening agent (1) 30Stain-preventing agent (3) 32 Guanidine picolinate 360 Potassiumquinolinate 45 First layer Gelatin 280 Water-soluble polymer (1) 12Anionic surfactant (1) 14 Sodium metaborate 35 Hardener (1) 185 Base (1)Polyethylene-Laminated Paper Support (thickness 215 μm)

The coated amount of dispersion of latex is in terms of the coatedamount of solid content of latex.

-   Water-soluble polymer (1)    -   Sumikagel L5-H (trade name: manufactured by Sumitomo Kagaku Co.,        Ltd. )-   Water-soluble polymer (2)    -   Dextran (molecular weight 70,000)-   Water-soluble polymer (3)    -   κ(kappa)-Carrageenan (trade name: manufactured by Taito Co.)-   Water-soluble polymer (4)    -   MP Polymer MP-102 (trade-name: manufactured by by Kuraray Co.-   Dispersion of latex (1)    -   LX-438 (trade name: manufactured by Nippon Zeon Co.)-   Matt agent (1)    -   SYLOID79 (trade name: manufactured by Fuji Davisson Kagaku Co.

Then, a light-sensitive material for heat-development was produced bythe following method.

First, the manner of forming a light-sensitive silver halide emulsionwill be described. Light-sensitive silver halide emulsion (1) (emulsionfor the fifth layer (680 nm light-sensitive layer))

A (I) solution and a (II) solution having compositions shown in Table 5were simultaneously added to a vigorously-stirred aqueous solutionhaving a composition shown in Table 4 over 19 minutes. After 5 minutesfrom the addition, a (III) solution having a composition shown in Table5 was added thereto over 33 minutes, and a (IV) solution having acomposition shown in Table 5 was added thereto over 33 minutes 30seconds.

TABLE 4 Composition H₂O 620 ml Lime-processed gelatin   20 g KBr  0.3 gNaCl   2 g Silver halide solvent {circle around (1)} 0.03 g Sulfuricacid (0.5 mol/l)  16 ml Temperature 45° C.

TABLE 5 Solution (I) Solution (II) Solution (III) Solution (IV) AgNO₃  30 g none   70 g none NH₄NO₃ 0.125 g none 0.375 g none KBr none 13.7 gnone 44.1 g NaCl none  3.6 g none  2.4 g K₂IrCl₆ none none none 0.039 mgTotal water to water to water to water to volume make make make make 126ml 132 ml 254 ml 252 ml

Further, after 15 min from the start of addition of solution (III), 150ml of an aqueous solution containing 0.350% of sensitizing dye {circlearound (1)} was added over 27 min.

After washing with water and desalting (that was carried out usingSettling Agent a, at a pH of 3.7 to 4.1) in a usual manner, 22 g oflime-processed ossein gelatin was added, and after adjusting the pH andpAg to 6.0 and 7.9 respectively, the chemical sensitization was carriedout at 60° C. The compounds used in the chemical sensitization are shownin Table 6. In this way, 630 g of a monodisperse cubic silverchlorobromide emulsion having a deviation coefficient of 10.2% and anaverage grain size of 0.20 μm was obtained.

TABLE 6 Chemicals used in chemical sensitization Added amount4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 0.36 g Sodium thiosulfate 6.75mg Antifoggant {circle around (1)} 0.11 g Antiseptic {circle around (1)}0.07 g Antiseptic {circle around (2)} 3.13 g

Light-Sensitive Silver Halide Emulsion (2) (Emulsion for the Third Layer(750 nm Light-Sensitive Layer))

A (I) solution and a (II) solution having compositions shown in Table 8were simultaneously added to a vigorously-stirred aqueous solutionhaving a composition shown in Table 7 over 18 minutes. After 5 minutesfrom the addition, a (III) solution having a composition shown in Table8 was added thereto over 24 minutes, and a (IV) solution having acomposition shown in Table 8 was added thereto over 24 minutes 30seconds.

TABLE 7 Composition H₂O 620 ml Lime-processed gelatin   20 g KBr  0.3 gNaCl   2 g Silver halide solvent {circle around (1)} 0.03 g Sulfuricacid (0.5 mol/l)  16 ml Temperature 46° C.

TABLE 8 Solution (I) Solution (II) Solution (III) Solution (IV) AgNO₃ 30.0 g none  70.0 g none NH₄NO₃ 0.125 g none 0.375 g none KBr none 13.7g none  44.1 g NaCl none  3.6 g none  2.4 g K₄[Fe(CN)₆] none none none0.065 g K₂IrCl₆ none none none 0.04 mg Total water to water to water towater to volume make make make make 126 ml 131 ml 280 ml 289 ml

After washing with water and desalting (that was carried out usingSettling Agent b at a pH of 3.9) in a usual manner, 22 g oflime-processed ossein gelatin from which calcium had been removed (thecalcium content: 150 ppm or less) was added, re-dispersing was made at40° C., 0.39 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added,and the pH and pAg were adjusted to 5.9 and 7.8 respectively. Thereafterthe chemical sensitization was carried out at 70° C. using the chemicalsshown in Table 9. At the end of the chemical sensitization, SensitizingDye {circle around (2)} in the form of a methanol solution (the solutionhaving the composition shown in Table 10) was added. After the chemicalsensitization, the temperature was-lowered to 40° C. and then 200 g of agelatin dispersion of the later described Stabilizer {circle around (1)}was added, followed by stirring well, and kept in a casing. In this way,938 g of a monodisperse cubic silver chlorobromide emulsion having adeviation coefficient of 12.6% and a average grain size of 0.25 μm wasobtained. In this connection, the emulsion for a 750 nm light-sensitivelayer had spectral sensitivity of the J-band type.

TABLE 9 Added Chemicals used in chemical sensitization amount4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 0.39 g Triethylthiourea  3.3mg Nucleic acid decomposition product 0.39 mg NaCl 0.15 g Kl 0.12 gAntifoggant {circle around (2)} 0.10 g Antiseptic {circle around (1)}0.07 g

TABLE 10 Added Composition of dye solution amount Sensitizing dye{circle around (2)} 0.19 g Methanol 18.7 ml

Light-Sensitive Silver Halide Emulsion (3) (Emulsion for the First Layer(810 nm Light-Sensitive Layer))

A (I) solution and a (II) solution having compositions shown in Table 12were simultaneously added to a vigorously-stirred aqueous solutionhaving a composition shown in Table 11 over 18 minutes. After 5 minutesfrom the addition, a (III) solution having a composition shown in Table12 was added thereto over 24 minutes, and a (IV) solution having acomposition shown in Table 12 was added thereto over 24 minutes 30seconds.

TABLE 11 Composition H₂O 620 ml Lime-processed gelatin   20 g KBr  0.3 gNaCl   2 g Silver halide solvent {circle around (1)} 0.03 g Sulfuricacid (0.5 mol/l)  16 ml Temperature 50° C.

TABLE 12 Solution (I) Solution (II) Solution (III) Solution (IV) AgNO₃30.0 g none 70.0 g none KBr none 13.7 g none 44.1 g NaCl none  3.6 gnone  2.4 g K₄[Fe(CN)₆] none none none 0.04 g K₂IrCl₆ none none none0.02 mg Total water to water to water to water to volume make 180 mlmake 181 ml make 242 ml make 250 ml

After washing with water and desalting (that was carried out usingSettling Agent a, at a pH of 3.8) in a usual manner, 22 g oflime-processed ossein gelatin was added, and after adjusting the pH andpAg to 7.4 and 7.8 respectively, the chemical sensitization was carriedout at 60° C. The compounds used in the chemical sensitization are shownin Table 13. Further, in the last of chemical sensitization, a solutionof a sensitizing dye {circle around (3)} in methanol was added (in thesame way as the sensitizing dye {circle around (2)} shown in Table 10).The yield of the resulting emulsion was 683 g. The emulsion was amonodispersion cubic silver chlorobromide emulsion of which thecoefficient of variation was 9.7% and the average grain size was 0.32μm.

TABLE 13 Added Chemicals used in chemical sensitization amount4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 0.38 g Triethylthiourea  3.1mg Antifoggant {circle around (2)} 0.19 g Antiseptic {circle around (1)}0.07 g Antiseptic {circle around (2)} 3.13 g

Preparation of Silver Chloride Fine-Grain Emulsion (Added to the FirstLayer (810 nm Light-Sensitive Layer))

A (I) solution and a (II) solution having compositions shown in Table 15were simultaneously added to a vigorously-stirred aqueous solutionhaving a composition shown in Table 14 over 4 minutes. After 3 minutesfrom the addition, a (III) solution and a (IV) solution havingcompositions shown in Table 15 were added thereto over 8 minutes.

TABLE 14 Composition H₂O 3770 ml Lime-processed gelatin  60 g NaCl 0.8 gTemperature 38° C.

TABLE 15 Solution (I) Solution (II) Solution (III) Solution (IV) AgNO₃300 g none 300 g none NH₄NO₃  10 g none  10 g none NaCl none 108 g none104 g Total water to water to water to water to volume make 940 ml make940 ml make 1170 ml make 1080 ml

After washing with water and desalting (that was carried out using theabove-shown Settling Agent a at a pH of 3.9) in a usual manner, 132 g oflime-processed ossein gelatin was added, re-dispersing was made at 35°C., 0.39 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added, andthe pH was adjusted to 5.7, to obtain silver chloride fine-grainemulsion. The yield of the resulting silver chloride fine-grain emulsionwas 3,200 g, whose average grain size was 0.10 μm.

The preparation method of a gelatin dispersion of colloidal silver isdescribed below.

To a well-stirred aqueous solution having the composition shown in Table16, was added a Solution having the composition shown in Table 17, over24 min. Thereafter, the washing with water using the above-shownSettling Agent a was carried out, then 43 g of lime-processed osseingelatin was added, and the pH was adjusted to 6.3. In this way, 512 g ofa dispersion having average grain size of 0.02 μm, and containing silver2% and gelatin 6.8% was obtained.

TABLE 16 Composition H₂O 620 ml Dextrin 16 g NaOH (5 mol/l)  41 mlTemperature 30° C.

TABLE 17 Composition H₂O 135 ml AgNO₃ 17 g

The preparation methods of gelatin dispersions of hydrophobic additivesare described below.

Gelatin dispersions of a yellow coupler and a built-in developing agent,a magenta coupler and a built-in developing agent, and, a cyan couplerand a built-in developing agent, whose formulations are shown in Table18, were prepared, respectively. That is, the oil phase components weredissolved by heating to about 70° C., to form a uniform solution, and tothe resultant solution, were added the aqueous phase components that hadbeen heated to about 60° C., followed by stirring to mix and dispersingby a homogenizer for 10 min at 10,000 rpm. To the resultant dispersion,was added additional water, followed by stirring, to obtain a uniformdispersion.

TABLE 18 Composition of dispersion Yellow Magenta Cyan Oil phase Yellowcoupler {circle around (1)}  6.97 g none none Cyan coupler {circlearound (1)} none none 6.63 g Magenta coupler {circle around (1)} none 7.14 g none Developing agent {circle around (1)}  5.58 g  5.71 g 5.30 gAuxiliary developing  0.51 g  0.51 g 0.51 g agent {circle around (1)}Antifoggant {circle around (3)} none  0.03 g 0.03 g Antifoggant {circlearound (4)}  0.64 g  0.08 g none Antifoggant {circle around (5)}  0.30 gnone none Surfactant {circle around (1)}  0.2 g  0.2 g  0.2 gHigh-boiling solvent {circle around (1)}  7.0 g  7.0 g  7.0 g Dye (a) 0.59 g none 0.14 g Water 0.2 ml none 0.3 ml Ethyl acetate  16 ml 16 ml 16 ml Aqueous Lime-processed gelatin  10.0 g  10.0 g 10.0 g phaseCalcium nitrate  0.05 g  0.04 g 0.05 g Zinc nitrate none  0.08 g noneCarboxymethyl cellulose none none 0.07 g Water  35 ml 31 ml  33 ml Water(after emulsification)  40 ml 43 ml  31 ml Antiseptic {circle around(1)} 0.003 g 0.002 g 0.03 g

A gelatin dispersion of Antifoggants {circle around (4)} and {circlearound (6)} and Auxiliary developing agent {circle around (1)} whoseformulation is shown in Table 19 was prepared. That is, the oil phasecomponents were dissolved by heating to about 60° C. to form a solution,and to the resultant solution, were added the aqueous phase componentsthat had been heated to about 60° C., and after stirring and mixingthem, the resultant mixture was dispersed for 10 min at 10,000 rpm by ahomogenizer, to obtain a uniform dispersion.

TABLE 19 Composition of dispersion Oil phase Antifoggant {circle around(4)} 1.0 g Antifoggant {circle around (6)} 0.8 g Auxiliary developingagent {circle around (1)} 0.1 g High-boiling organic solvent {circlearound (2)} 2.3 g High-boiling organic solvent {circle around (1)} 0.2 gSurfactant {circle around (1)} 0.5 g Surfactant {circle around (2)} 0.5g Ethyl acetate 10.0 ml Aqueous phase Lime-processed gelatin 10.0 gAntiseptic {circle around (1)} 0.004 g Calcium nitrate 0.1 g Water 35.0ml Additional Water 46 ml

High-boiling organic solvent {circle around (2)}

-   -   C₂₆H_(46.9)Cl_(7.1)    -   EMPARA 40 (trade name: manufactured by Ajinomoto K. K.)

A gelatin dispersion of Reducing Agent {circle around (1)} whoseformulation is shown in Table 20 was prepared. That is the oil phasecomponents were dissolved by heating to about 60° C. to form a solution,and to the resultant solution, were added the aqueous phase componentsthat had been heated to about 60° C., and after stirring and mixingthem, the resultant mixture was dispersed for 10 min at 10,000 rpm by ahomogenizer, to obtain a uniform dispersion. From the thus obtaineddispersion, ethyl acetate was removed off using a vacuum organic solventremoving apparatus.

TABLE 20 Composition of dispersion Oil phase Reducing agent {circlearound (1)} 7.5 g High-boiling organic solvent {circle around (3)} 4.7 gSurfactant {circle around (1)} 1.9 g Ethyl acetate 14.4 ml Aqueous phaseAcid-processed gelatin 10.0 g Antiseptic {circle around (1)} 0.002 gAntiseptic {circle around (3)} 1.004 g Calcium nitrate 2.1 g Water 136.7ml

High-boiling organic solvent {circle around (3)}

-   -   (C₄H₉(C₂H₅)CHCH₂O)₃—P═O

A dispersion of Polymer Latex (a) whose formulation is shown in Table 21was prepared. That is, while a mixed solution of Polymer Latex (a),Surfactant {circle around (3)}, and water whose amounts are shown inTable 21 was stirred, Anionic Surfactant {circle around (1)} was addedthereto, over 10 min, to obtain a uniform dispersion. The resultingdispersion was repeatedly diluted with water and concentrated using aultrafiltration module (Ultrafiltration Module: ACV-3050, trade name,manufactured by Asahi Chemical Industry Co., Ltd.), to bring the saltconcentration of the dispersion to 1/9, thereby obtaining the intendeddispersion.

TABLE 21 Composition of dispersion Polymer Latex (a) aqueous solution 108 ml (solid content 13%) Surfactant {circle around (3)}  20 g Anionicsurfactant {circle around (1)} aqueous solution (5%)  600 ml Water 1232ml

A gelatin dispersion of Stabilizer {circle around (1)} whose formulationis shown in Table 22 was prepared. That is, the oil phase componentswere dissolved at room temperature to form a solution, and to theresultant solution, were added the aqueous phase components that hadbeen heated to about 40° C., and after stirring and mixing them, theresultant mixture was dispersed for 10 min at 10,000 rpm by ahomogenizer. To the resultant dispersion, was added additional water,followed by stirring, thereby obtaining a uniform dispersion.

TABLE 22 Composition of dispersion Oil phase Stabilizer {circle around(1)} 4.0 g Sodium hydroxide 0.3 g Methanol 62.8 g High-boiling organicsolvent {circle around (6)} 0.9 g Aqueous phase Gelatin from whichcalcium had been 10 g removed (Ca content 100 ppm or less) Antiseptic{circle around (1)} 0.04 g Water 320.5 ml

A gelatin dispersion of zinc hydroxide was prepared according to theformulation shown in Table 23. That is, after the components were mixedand dissolved, dispersing was carried out for 30 min in a mill, usingglass beads having an average particle diameter of 0.75 mm. Then theglass beads were separated and removed off, to obtain a uniformdispersion. (Zinc hydroxide having a grain size of 0.25 μm was used.)

TABLE 23 Composition of dispersion Zinc hydroxide 15.9 g Carboxymethylcellulose  0.7 g Poly (sodium acrylate) 1.07 g Lime-processed gelatin 4.2 g Water  100 ml High-boiling organic solvent {circle around (1)} 0.4 g

The preparation method of a gelatin dispersion of a matt agent that wasto be added to the protective layer is described.

A solution containing PMMA dissolved in methylene chloride was added,together with a small amount of a surfactant, to gelatin, and they werestirred and dispersed at high speed. Then the methylene chloride wasremoved off using, a vacuum solvent removing apparatus, to obtain auniform dispersion having an average particle size of 4.3 μm.

Using the above materials, Light-Sensitive Element 101 shown in Tables24 to 25 was prepared.

TABLE 24 Constitution of Main Materials of Light-Sensitive Element 101Number Name of Added amount of layer layer Additive (mg/m²) SeventhProtective Acid-processed gelatin 442 layer layer Reducing agent {circlearound (1)} 47 High-boiling organic solvent {circle around (1)} 30Colloidal silver grains 2 Matting agent(PMMA resin) 17 Surfactant{circle around (1)} 16 Surfactant {circle around (4)} 9 Surfactant{circle around (5)} 2 Calcium nitrate 5 Sixth IntermediateLime-processed gelatin 862 layer layer Zinic hydroxide 577 Antifoggant{circle around (4)} 86 Antifoggant {circle around (6)} 69 Auxiliarydeveloping agent {circle around (1)} 9 High-boiling organic solvent{circle around (1)} 17 High-boiling organic solvent {circle around (2)}198 Surfactant {circle around (1)} 43 Surfactant {circle around (2)} 43Dispersion of Polymer Latex a 5 Water-soluble polymer {circle around(1)} 5 Calcium nitrate 17 Fifth 680 nm- Lime-processed gelatin 588 layerlight- Light-sensitive silver halide 301 sensitive emulsion(1) layerMagenta coupler {circle around (1)} 420 High-boiling organic solvent{circle around (1)} 412 Developing agent {circle around (1)} 336Antifoggant {circle around (3)} 2 Antifoggant {circle around (4)} 5Surfactant {circle around (1)} 12 Auxiliary developing agent {circlearound (1)} 30 Water-soluble polymer {circle around (1)} 11 ForthIntermediate Lime-processed gelatin 862 layer layer Zinic hidroxide 271Antifoggant {circle around (6)} 7 Auxiliary developing agent {circlearound (1)} 57 High-boiling organic solvent {circle around (1)} 101High-boiling organic solvent {circle around (2)} 9 Surfactant {circlearound (1)} 21 Surfactant {circle around (2)} 21 Water-soluble polymer{circle around (1)} 4 Calcium nitrate 6 Dispersion of Polymer Latex a 5

TABLE 25 Number Name of Added amount of layer layer Additive (mg/m²)Third 750 nm- Lime-processed gelatin 588 layer light- Light-sensitivesilver 106 sensitive halide emulsion (2) layer Stabilizer {circle around(1)} 8 Developing agent {circle around (1)} 312 Cyan coupler {circlearound (1)} 390 Dye (a) 13 High-boiling organic solvent {circle around(1)} 412 Auxiliary developing agent {circle around (1)} 30 Antifoggant{circle around (3)} 2 Surfactant {circle around (1)} 12 Carboxymethylcellulose 7 Water-soluble polymer {circle around (1)} 11 SecondIntermediate Lime-processed gelatin 862 layer layer Antifoggant {circlearound (6)} 7 High-boiling organic solvent {circle around (1)} 101High-boiling organic solvent {circle around (2)} 9 Auxiliary developingagent {circle around (1)} 57 Surfactant {circle around (1)} 21Surfactant {circle around (2)} 21 Water-soluble polymer {circle around(2)} 25 Calcium nitrate 6 First 810 nm- Lime-processed gelatin 588 layerlight- Light-sensitive silver 311 sensitive halide emulsion (3) layerUltrafine-grain silver chloride 30 emulsion Stabilizer {circle around(1)} 8 Yellow coupler {circle around (1)} 410 Developing agent {circlearound (1)} 328 Dye (a) 42 High-boiling organic solvent {circle around(1)} 412 Surfactant{circle around (1)} 12 Auxiliary developing agent{circle around (1)} 30 Antifoggant {circle around (4)} 38 Antifoggant{circle around (5)} 18 Water-soluble polymer {circle around (2)} 40Hardener {circle around (1)} 45 Support (Paper support whose bothsurfaces were laminated with polyethylene: thickness 135 μm)

Hardener {circle around (1)}

-   -   CH₂═CHSO₂CH₂SO₂CH═CH₂

Then, light-sensitive elements 102-105 were formed in the same manner asthe light-sensitive element 101, except that the developing agent{circle around (1)} and the yellow coupler {circle around (1)} shown inTable 18 were changed to each combination shown in Table 26.Furthermore, light-sensitive elements 106-109 were formed in the samemanner as the light-sensitive element 101, except that the developingagent {circle around (1)} and the magenta coupler {circle around (1)}shown in Table 18 were changed to each combination shown in Table 27.

TABLE 26 Light-sensitive material Yellow coupler Developing agentRemarks 101 Yellow coupler {circle around (1)} Developing Comparativeagent {circle around (1)} example 102 Yellow coupler {circle around (1)}R-22 This invention 103 Cp-1 R-22 This invention 104 Cp-2 R-25 Thisinvention 105 Cp-3 R-28 This invention

TABLE 27 Light-sensitive material Magenta coupler Developing agentRemarks 101 Magenta coupler {circle around (1)} Developing Comparativeagent {circle around (1)} example 106 Magenta coupler {circle around(1)} R-22 This invention 107 Cp-6 R-22 This invention 108 Cp-7 R-26 Thisinvention 109 Cp-10 R-31 This invention

Each of these light-sensitive materials obtained in the above-mentionedway was combined with the dye fixation material R101. From eachcombination, an image was outputted, using PG-3000 (trade name) made byFuji Photo Film Co., Ltd. Heating temperature was 83° C., and processingtime was 20 seconds or 35 seconds.

The images outputted from the light-sensitive materials 102-109 werevivid color images. Thus, when the compound of the present invention wasused, the sharpness of the resultant image was excellent.

A reflection densitometer X-rite 304 (trade name) made by X-rite Companywas used to measure Dmax (highest density, and Dmin (lowest density) ofthe thus obtained images.

The results are shown in Table 28.

TABLE 28 Light- 20 seconds 35 seconds sensitive processing processingmaterial Dmax Dmin Dmax Dmin Remarks 101 0.93 0.13 1.56 0.15 Comparativeexample (yellow) 102 1.54 0.13 2.03 0.14 This invention (yellow) 1031.69 0.14 2.15 0.15 This invention (yellow) 104 1.77 0.12 2.18 0.13 Thisinvention (yellow) 105 1.99 0.12 2.33 0.13 This invention (yellow) 1011.25 0.14 1.78 0.19 Comparative example (magenta) 106 2.18 0.14 2.740.15 This invention (magenta) 107 2.01 0.12 2.47 0.15 This invention(magenta) 108 2.1 0.15 2.58 0.16 This invention (magenta) 109 1.94 0.142.39 0.15 This invention (magenta)

As is apparent from Table 28, it can be understood that thelight-sensitive materials using the compound of the present inventionexhibited good photographic performances in a short time. The resultantimages were stable under conditions of high temperature and humidity andthe like.

The images obtained from the light-sensitive materials were irradiatedwith Xenon light having an illumination of 170,000 lux for a week. Withrespect to the portions having the magenta density or yellow density of1.0, dye remaining rates were obtained. The results are shown in Table29.

TABLE 29 Light-sensitive Residual rate of dye material (%) Remarks 10170.2 Comparative example (yellow) 102 85.6 This invention (yellow) 10381.2 This invention (yellow) 104 77.9 This invention (yellow) 105 83.5This invention (yellow) 101 58.5 Comparative example (magenta) 106 66.7This invention (magenta) 107 80.1 This invention (magenta) 108 82.6 Thisinvention (magenta) 109 84.1 This invention (magenta)

The results in Tables 28 and 29 demonstrate that the light-sensitivematerials using the compound of the present invention had both of highdeveloped color density and excellent fastness to light.

Example 1-2

In the method described in Example 1 of JP-A-09-152702, the developingagents (Exemplified compounds R-22, R-23, R-25, R-10, R-11 and R-30) ofthe present invention were used in place of the compound example D-7. Asa consequence, images were obtained which were excellent in colorformation efficiency and had good storage stability, similar in theabove Examples 1-1.

Example 1-3

A light-sensitive element (Sample 301) was produced by the followingmethod.

First, the method of preparing silver halide emulsions will bedescribed.

Eight kinds of silver halide emulsion grains (Emulsion-A to Emulsion-F)and Emulsion-T and Emulsion-U, which will be described below, wereprepared by the following emulsion grain preparinq method.

Preparation of Emulsion A (Octahedron Internal-Latent-Image-Type DirectPositive Emulsion):

To 1000 ml of an aqueous gelatin solution containing 0.05 M of potassiumbromide, 1 g of 3,6-dithia-1,8-octanediol, 0.034 mg of lead acetate, and60 g of deionized gelatin containing 100 ppm or less of Ca, was added300 ml of 0.4 M aqueous silver nitrate solution over 40 minutes with thetemperature being kept at 75° C., while in a controlled double jetmethod of adding the aqueous silver aqueous nitrate solution and a 0.4 Maqueous potassium bromide solution, the addition rate of the aqueouspotassium bromide solution was adjusted in such a manner that pBr wouldbe 1.60.

When the addition was finished, octahedron silver bromide crystal, whichwill be referred to as core grains hereinafter, was generated. The coregrains had an average grain diameter (sphere equivalent diameter) ofabout 0.7 μm, and the grain sizes thereof were substantially even.

Then, chemical sensitization of core was performed under the followingconditions.

-   1. Tank: a tank, the metal surface of which had a coating layer    (thickness: 120 μm) made of a fluorine resin material FEP    (polytetrafluoroethylene; Teflon, trade name) made by Du Pont. The    tank had a semi-ball shaped bottom.-   2. Stirring fan: a propeller of a jointless integration-type, the    metal surface of which was coated with Teflon.

To a preparation solution of the Emulsion-A were added 1 mg of sodiumthiosulfate, and 3 ml of an aqueous solution of 90 mg of potassiumtetrachloroaurate and 1.2 g of potassium bromide in 1000 ml of water,and then the solution was heated at 75° C. for 80 minutes to conductchemical sensitization. To the thus chemically-sensitized emulsionsolution was added 0.15 M of potassium bromide. Thereafter, in the samemanner as in the preparation of the core grains, to the resultantsolution was added 670 ml of a 0.9 M aqueous silver nitrate solutionover 70 minutes with the temperature being kept at 75° C., while in acontrolled double jet method of adding the aqueous silver nitratesolution and a 0.9 M aqueous potassium bromide solution, the additionrate of the aqueous potassium bromide solution was adjusted in such amanner that pBr would be 1.30.

This emulsion was washed with water in a usual flocculation manner, andthen thereto were added the above-mentioned gelatin, 2-phenoxyethanoland methyl p-hydroxybenzoate, to obtain octahedron silver bromidecrystal, which will be referred to as internal-latent-image-typecore/shell grains hereinafter, having an average grain diameter (sphereequivalent diameter) of about 1.2 μm. The internal-latent-image-typecore/shell grains had a substantially even grain size.

Then, to the internal-latent-image-type core/shell grain emulsion, wasadded 3 ml of an aqueous solution of 100 mg of sodium thiosulfate and 40mg of sodium tetraborate in 1000 ml of water, and then thereto was added14 mg of poly(N-vinylpyrrolidone). The resultant emulsion was heated andripened at 60° C. Thereafter, 0.005 M of potassium bromide was addedthereto, to prepare an octahedron internal-latent-image-type directpositive emulsion.

Preparation of Emulsions-B to -F (Octahedron Internal-Latent-Image-TypeDirect Positive Emulsions):

In the method of preparation of the Emulsion-A, the times for adding theaqueous silver nitrate solution and the aqueous potassium bromidesolution were changed and the amounts of the chemicals added werechanged, to obtain octahedron internal-latent-image-type direct positivesilver halide emulsions, each of which had an average grain diameter(sphere equivalent diameter) shown in Table. 30. The emulsions had asubstantially even grain size.

TABLE 30 Name of emulsion Average grain diameter μm B 0.93 C 1.20 D 0.94E 0.74 F 0.66Preparation of Emulsion-T (Hexagonal Tabular Internal-Latent-Image-TypeDirect Positive Emulsion):

To 1.2 liter of an aqueous gelatin solution containing 0.05 M ofpotassium bromide and 0.7% by weight of gelatin having an averagemolecular weight of 100,000 or less, were simultaneously added 33 ml ofa 1.4 M aqueous silver nitrate solution containing the above-mentionedgelatin and 33 ml of a 2M aqueous potassium bromide solution over 1minute by a double jet method while vigorously stirred. During thisaddition, the aqueous gelatin solution was kept at 30° C. Furthermore,thereto was added 300 ml of a gelatin solution containing 10% by mass ofdeionized gelatin having 100 ppm or less of Ca, and the temperature ofthe resultant emulsion was raised to 75° C.

Then, 40 ml of a 0.9 M aqueous silver nitrate solution was added theretoover 3 minutes, and then a solution containing 25% by mass of ammonia inwater was added thereto. The emulsion was ripened at 75° C. to ripen.After the ripening, the ammonia was neutralized, and 5 mg oflead-acetate (in the form of an aqueous solution) was added thereto.Thereafter, a 1M aqueous silver nitrate solution and a 1M aqueouspotassium bromide solution were added thereto at a given acceleratedflow rate (the flow rate at the finish time was six times larger thanthat at the initial time) by a double jet method while pBr was kept at2.5. The volume of the aqueous silver nitrate solution to be used was500 ml.

The thus produced grains, which will be referred to as core grains, werewashed with water in a usual flocculation manner, and then thereto wereadded gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate, to obtain750 g of hexagonal tabular core grains.

The resultant hexagonal tabular core grains had an average diameter ofcircle equivalent to projected area of 0.9 μm, and an average thicknessof 0.20 μm. The hexagonal tabular grains occupied 95% of the totalprojection area.

Chemical sensitization of core was performed under the followingconditions.

-   1. Tank: a tank, the metal surface of which had a coating layer    (thickness: 120 μm) made of a fluorine resin material FEP made by-Du    Pont. The tank had a semi-ball shaped bottom.-   2. Stirring fan: a propeller of a jointless integration-type, the    metal surface of which was coated with Teflon.

To 200 g of the hexagonal tabular core emulsion, were added 1300 ml ofwater, 0.11 M of potassium bromide, and 40 g of deionized gelatin, andthen the temperature of the mixture was raised to 75° C. Thereafter,thereto were added 0.3 g of 3,6-dithia-1,8-octanediol, 10 mg of sodiumbenzenethiosulfate, 2.4 ml of an aqueous solution wherein 90 mg ofpotassium tetrachloroaurate and 1.2 g of potassium bromide weredissolved into 1000 ml of water, and 15 mg of lead acetate (in the formof an aqueous solution), and then the mixture was heated at 75° C. for180 minutes to perform chemical sensitization. In the same manner as thetime of preparing the core grains, a 2M aqueous silver nitrate solutionand a 2.5M aqueous potassium bromide solution were added to the thuschemically-sensitized core grains at a given accelerated flow rate (theflow rate at the finish time was three times larger than that at theinitial time) by a double jet method, while the addition speed of theaqueous potassium bromide solution was adjusted so that pBr would be2.2. The volume of the aqueous silver nitrate solution to be used was810 ml.

Thereto was added 0.3 mole of potassium bromide, and then this emulsionwas washed with water in a usual flocculation manner. Gelatin was addedthereto. In this way, a hexagonal tabular internal-latent-image typecore/shell emulsion was obtained. The resultant hexagonal tabular grainshad an average diameter of circle equivalent to projected area of 2.0μm, an average thickness of 0.38 μm, and an average volume size of 1.3(μm)³. The hexagonal tabular grains occupied 88% of the total projectedarea.

Then, to this hexagonal tabular internal-latent-image type core/shellemulsion was added 15 ml of an aqueous solution wherein 10 mg of sodiumthiosulfate and 40 mg of sodium tetraborate were dissolved into 1000 mlof water. Furthermore, 20 mg of poly(N-vinylpyrrolidone) was addedthereto. The emulsion was heated at 70° C. for 100 minutes to performchemical sensitization of the surfaces of the grains. Thus, a hexagonaltabular internal-latent-image-type direct positive emulsion wasprepared. Preparation of Emulsion-U (hexagonal tabularinternal-latent-image-type direct positive emulsion):

When the outer shell of the Emulsion-T was formed, 0.15 mol % of iodidewas uniformly incorporated thereto and then the amount of the formedouter shell was increased. Thus, hexagonal tabular grains were obtained,which had an average diameter of circle equivalent to projected area of2.5 μm, an average grain thickness of 0.45 μm, and an average volumesize of 1.7 (μm)³, and which occupied 88% of the total projected area.

Then, thereto was added AgI fine-particle Emulsion-X in an amountcorresponding to 0.04 mol % of the silver amount required for theformation of the grains at the initial time of chemical sensitization ofthe shell of the hexagonal tabular internal-latent-image-type core/shellemulsion. Thereafter, the resultant emulsion was subjected to the sameshell chemical sensitization as in the case of the Emulsion-T, so as toprepare a hexagonal tabular internal-latent-image-type direct positiveemulsion.

Preparation of Emulsion-X (AgI Fine-Particle Emulsion)

To water were added 0.5 g of potassium iodide and 26 g of gelatin., Tothe solution, the temperature of which was kept at 35° C., were added 80ml of a silver nitrate solution containing 40 g of silver nitrate inwater and 80 ml of a solution containing 39 g of potassium iodide inwater over 5 minutes while the solution was stirred. At this time, eachof the addition flow rates of the aqueous silver nitrate solution andthe aqueous potassium iodide solution was set to 8 ml/minute at theinitial time of the addition. The addition flow rates were linearlyaccelerated so that the addition of 80 ml of each of the solutions wouldbe finished in 5 minutes.

After the formation of the grains was finished in this way, solublesalts were removed at 35° C. by a sedimentation method. Then, thetemperature of the resultant solution was raised to 40° C., and thenthereto were added 10.5 g of gelatin and 2.5 g of phenoxyethanol. The pHof the solution was adjusted to 6.8 with caustic sodium. The amount ofthe resultant emulsion was 730 g. The emulsion was monodispersive AgIfine grains having an average diameter of 0.015 μm.

The Emulsions-A to -F, -T and -U were used in the following manner toform a light-sensitive element (Sample 301) for comparison, havingstructures shown in Tables 31-35. Sensitizing dyes were added at thetime of the end of shell chemical sensitization in accordance with dyekinds, dispersion forms, addition temperatures, and amounts shown inTable 36.

TABLE 31 Constitution of Main materials for Light-Sensitive Element 301Coated Number of amount layer Name of layer Additive (g/m²) 24th layerProtective layer Matting agent (1) 0.3514 Gelatin 0.196 Surfactant (1) 4.01 × 10⁻³ Surfactant (2) 4.671 × 10⁻³ Surfactant (3) 9.398 × 10⁻³Additive (1) 8.710 × 10⁻³ Additive (5) 5.260 × 10⁻³ Additive (24) 6.789× 10⁻³ 23rd layer Ultraviolet Ultraviolet absorber (1) 8.252 × 10⁻²absorbing layer Ultraviolet absorber (2) 4.355 × 10⁻² Ultravioletabsorber (3) 1.146 × 10⁻² Surfactant (3) 1.241 × 10⁻² Additive (1) 1.213× 10⁻² Additive (5) 1.394 × 10⁻² Additive (24) 5.881 × 10⁻⁵ Additive(25) 1.164 × 10⁻⁴ Hardener (1) 7.462 × 10⁻² Hardener (2) 2.488 × 10⁻²Gelatin 0.299 22nd layer Blue-light- Internal-latent-image-type 0.460sensitive layer direct positive emulsion: U (high speed) Nucleatingagent (1) 5.124 × 10⁻⁶ Additive (22) 4.198 × 10⁻⁶ Additive (23) 1.542 ×10⁻⁶ Additive (24) 7.696 × 10⁻⁶ Additive (3) 4.804 × 10⁻³ Additive (4)1.405 × 10⁻² Additive (5) 3.818 × 10⁻⁶ Gelatin 0.513 21st layerBlue-light- Internal-latent-image-type 0.0745 sensitive layer directpositive emulsion: A (low speed) Internal-latent-image-type 0.0745direct positive emulsion: B Nucleating agent (1) 2.501 × 10⁻⁶ Additive(3) 3.735 × 10⁻³ Additive (5) 1.724 × 10⁻² Additive (24) 7.603 × 10⁻⁵Additive (1) 3.771 × 10⁻³ Surfactant (5) 7.750 × 10⁻³ Gelatin 0.309 20thlayer White reflection Titanium dioxide 0.4151 layer Additive (1) 7.667× 10⁻³ Surfactant (1) 9.354 × 10⁻⁵ Additive (5) 1.348 × 10⁻² Additive(24) 1.117 × 10⁻⁴ Additive (26) 8.384 × 10⁻³ Additive (8) 3.316 × 10⁻³Gelatin 0.254

TABLE 32 Number Coated of amount layer Name of layer Additive (g/m²)19th Yellow colored Color developing agent {circle around (1)} 0.348layer material layer Yellow coupler {circle around (1)} 0.317High-boiling organic solvent (1) 0.350 Surfactant (5) 1.700 × 10⁻²Additive (24) 1.496 × 10⁻³ Additive (1) 7.032 × 10⁻³ Gelatin 0.793 18thIntermediate Additive (10) 1.010 × 10⁻² layer layer Surfactant (1) 3.425× 10⁻⁴ Additive (1) 7.039 × 10⁻³ Additive (23) 1.605 × 10⁻² Additive(24) 6.540 × 10⁻⁵ Gelatin 0.332 17th Color mixing Color mixingprevention 0.312 layer prevented agent (1) layer Poly(methylmethacrylate) 0.538 Surfactant (5) 3.700 × 10⁻² Additive (1) 7.039 ×10⁻³ Additive (12) 0.383 Additive (26) 1.562 × 10⁻² Gelatin 0.640 16thGreen-light- Internal-latent-image-type 0.435 layer sensitive layerdirect positive emulsion: T (high speed) Nucleating agent (1) 2.391 ×10⁻⁶ Additive (22) 6.403 × 10⁻² Additive (23) 1.595 × 10⁻² Additive (3)7.988 × 10⁻² Additive (5) 3.687 × 10⁻² Additive (24) 2.161 × 10⁻²Additive (26) 2.623 × 10⁻³ Additive (1) 7.803 × 10⁻² Surfactant (5)3.792 × 10⁻² High-boiling organic solvent (2) 4.182 × 10⁻² Gelatin 0.61515th Green-light- Internal-latent-image-type 0.130 layer sensitive layerdirect positive emulsion: C (low speed) Internal-latent-image-type 0.130direct positive emulsion: D Nucleating agent (1) 1.843 × 10⁻⁶ Additive(3) 4.048 × 10⁻² Additive (22) 2.204 × 10⁻² Additive (23) 4.048 × 10⁻²Additive (24) 8.331 × 10⁻⁵ Additive (26) 1.329 × 10⁻³ Additive (5) 2.146× 10⁻² Additive (1) 4.094 × 10⁻³ Surfactant (5) 1.933 × 10⁻² Gelatin0.329

TABLE 33 Number Coated of Name of amount layer layer Additive (g/m²)14th Intermediate Additive (1) 6.989 × 10⁻³ layer layer Surfactant (1)2.822 × 10⁻⁴ Additive (5) 1.162 × 10⁻² Additive (24) 5.242 × 10⁻⁵Gelatin 0.266 13th Magenta Color developing agent {circle around (1)}0.272 layer colored Magenta coupler {circle around (1)} 0.303 materiallayer High-boiling organic solvent (1) 0.320 Additive (13) 8.462 × 10⁻⁴Additive (5) 1.740 × 10⁻² Additive (24) 5.653 × 10⁻⁴ Surfactant (5)1.820 × 10⁻² Additive (14) 2.039 × 10⁻² Additive (1) 8.247 × 10⁻³Gelatin 0.405 12th Intermediate Additive (10) 3.806 × 10⁻³ layer layerSurfactant (1) 3.002 × 10⁻⁴ Additive (1) 7.064 × 10⁻³ Gelatin 0.283 11thColor-mix Color mixing prevention 0.320 layer preventing agent (1) layerPoly(methyl methacrylate) 0.554 Surfactant (5) 3.806 × 10⁻² Additive (1)7.039 × 10⁻³ Additive (12) 0.554 Additive (26) 1.607 × 10⁻² Gelatin0.658 10th Red-light- Internal-latent-image-type 0.373 layer sensitivedirect positive emulsion: T layer Nucleating agent (1) 1.143 × 10⁻⁵(high speed) Additive (22) 4.231 × 10⁻² Additive (23) 1.555 × 10⁻²Additive (3) 9.488 × 10⁻³ Additive (4) 2.755 × 10⁻² Additive (5) 2.993 ×10⁻² Additive (24) 1.366 × 10⁻⁴ Additive (1) 3.420 × 10⁻³ Surfactant (5)2.454 × 10⁻² High-boiling organic solvent (2) 3.069 × 10⁻² Gelatin 0.487

TABLE 34 Number Coated of Name of amount layer layer Additive (g/m²) 9thRed-light- Internal-latent-image-type 0.083 layer sensitive directpositive emulsion: E layer Internal-latent-image-type 0.083 (low speed)direct positive emulsion: F Nucleating agent (1) 1.617 × 10⁻⁵ Additive(3) 7.489 × 10⁻³ Additive (4) 2.190 × 10⁻² Additive (5) 2.818 × 10⁻²Additive (24) 3.794 × 10⁻⁴ Additive (1) 5.963 × 10⁻³ Surfactant (5)1.554 × 10⁻² Gelatin 0.260 8th White Titanium dioxide 1.684 layerreflection Additive (1) 2.231 × 10⁻³ layer Surfactant (1) 3.794 × 10⁻⁴Additive (8) 1.345 × 10⁻³ Additive (5) 3.619 × 10⁻² Additive (24) 3.794× 10⁻⁴ Additive (26) 3.401 × 10⁻² Gelatin 0.655 7th Cyan colored Cyandye-releasing compound (1) 0.1031 layer material Cyan dye releasingcompound (2) 0.1852 layer High-boiling organic solvent (1) 8.403 × 10⁻²Additive (3) 1.106 × 10⁻² Additive (4) 3.234 × 10⁻² Additive (5) 9.989 ×10⁻³ Additive (6) 3.150 × 10⁻² Additive (24) 5.753 × 10⁻⁴ Additive (7)1.594 × 10⁻² Surfactant (4) 2.890 × 10⁻² Additive (9) 3.438 × 10⁻³Additive (1) 2.606 × 10⁻³ Hardener (3) 1.053 × 10⁻² Gelatin 0.364 6thIntermediate Surfactant (1) 2.136 × 10⁻² layer layer Additive (1) 1.170× 10⁻² Additive (5) 1.309 × 10⁻² Additive (24) 5.691 × 10⁻² Gelatin0.289 5th Shading Carbon black 1.552 layer layer Surfactant (1) 2.578 ×10⁻² Additive (1) 1.331 Additive (5) 7.685 × 10⁻² Additive (14) 9.354 ×10⁻² Additive (26) 2.701 × 10⁻² Gelatin 0.878

TABLE 35 Number of Coated amount layer Name of layer Additive (g/m²) 4thlayer Intermediate Surfactant (1)  6.77 × 10⁻⁴ layer Additive (1) 9.029× 10⁻³ Additive (5) 1.278 × 10⁻² Additive (24) 5.691 × 10⁻⁵ Hardener (1)2.132 × 10⁻² Hardener (2) 7.107 × 10⁻⁵ Gelatin  0.289 Third WhiteTitanium dioxide 17.905 layer reflection Surfactant (1) 1.464 × 10⁻²layer Additive (1)  0.144 Additive (26) 2.595 × 10⁻² Gelatin  2.802Second Intermediate Surfactant (7) 1.286 × 10⁻² layer layer Additive (5)1.167 × 10⁻² Additive (24) 8.167 × 10⁻⁵ Gelatin  0.399 First Image-Polymer mordant (1)  2.820 layer receiving Additive (17)  0.2839 layerAdditive (5) 8.172 × 10⁻² Additive (24) 5.721 × 10⁻⁴ Gelatin  2.795Support (90 μm of polyethylene terephthalate undercoated and containingtitanium dioxide for preventing light piping) Backing Curl Ultravioletabsorber (4)  0.40 layer controlling Ultraviolet absorber (5)  0.10layer Diacetylcellulose  4.20 (Acetylation degree 51%) Additive (18) 0.25 Barium stearate  0.11 Hardener (4)  0.50

TABLE 36 Content of sensitizing dyes per 1 kg of the emulsion Amount ofdye Number Name of Sensitizing dye Temperature g/1 kg of layer emulsiontype Dye dispersion form when added emulsion (9) Aqueous solution 70° C.9.38 × 10⁻² 22 U (8) Aqueous solution 1.19 × 10⁻¹ (9) Aqueous solution60° C. 6.50 × 10⁻² 21 A (8) Aqueous solution 1.47 × 10⁻¹ (9) Aqueoussolution 60° C. 7.31 × 10⁻² 21 B (8) Aqueous solution 1.66 × 10⁻¹ (7)Gelatin dispersion 60° C. 1.18 × 10⁻¹ 16 T (4) Gelatin dispersion 2.94 ×10⁻³ (6) Dispersion of 9.23 × 10⁻² water/organic solvent with surfactant(7) Gelatin dispersion 40° C. 6.49 × 10⁻² 15 C (4) Gelatin dispersion1.62 × 10⁻³ (6) Dispersion of 4.85 × 10⁻² water/organic solvent withsurfactant (7) Gelatin dispersion 40° C. 7.34 × 10⁻² 15 D (4) Gelatindispersion 1.83 × 10⁻³ (6) Dispersion of 5.69 × 10⁻² water/organicsolvent with surfactant (5) Aqueous solution 60° C. 3.10 × 10⁻² (4)Gelatin dispersion 2.26 × 10⁻² 10 T (3) Gelatin dispersion 2.26 × 10⁻²(2) Gelatin dispersion 2.79 × 10⁻³ (1) Gelatin dispersion 9.20 × 10⁻²(5) Aqueous solution 60° C. 1.63 × 10⁻² (4) Gelatin dispersion 1.34 ×10⁻² 9 E (3) Gelatin dispersion 1.34 × 10⁻² (2) Gelatin dispersion 1.91× 10⁻³ (1) Gelatin dispersion 6.32 × 10⁻² (5) Aqueous solution 50° C.1.17 × 10⁻² (4) Gelatin dispersion 8.90 × 10⁻³ 9 F (3) Gelatindispersion 8.90 × 10⁻³ (2) Gelatin dispersion 1.32 × 10⁻³ (1) Gelatindispersion 4.37 × 10⁻²

Molecular weight: 728.77 Molecular formula: C₂₅H₂₆Cl₂N₂O₆S₄.C₅H₅N₁Sensitizing dye (1)

Molecular weight: 686.24 Molecular formula: C₃₀H₃₁Cl₁N₂O₇S₃.NA₁Sensitizing dye (3)

Molecular weight: 782.09 Molecular formula: C₃₃H₃₂N₂O₆S₄.C₆H₁₅N₁Sensitizing dye (2)

Molecular weight: 751.89 Molecular formula: C₃₅H₃₂N₂O₈S₂.C₅H₅N₁Sensitizing dye (7)

Molecular weight: 707.96 Molecular formula: C₃₃H₃₆N₂O₇S₃.K₁ Sensitizingdye (4)

Molecular weight: 742.57 Molecular formula: C₃₀H₂₅Cl₂F₇N₆O₃S₁Sensitizing dye (6)

Molecular weight: 707.96 Molecular formula: C₂₆H₂₆N₂O₇S₄.C₆H₅N₁Sensitizing dye (9)

Molecular weight: 724.83 Molecular formula: C₂₃H₂₄Cl₂N₂O₆S₄.C₆H₁₅N₁Sensitizing dye (5)

Molecular weight: 752.00 Molecular formula: C₃₂H₃₀N₂O₇S₃.C₆H₁₅N₁Sensitizing dye (8)

Additive (8)

-   -   Carboxymethyl cellulose    -   (CMC CELLOGEN 6A, trade name, manufactured by Dai-ichi Kogyo        Seiyaku Co., Ltd.)

Additive (9)

-   -   Polyvinyl alcohol (PVA-220E, trade name)    -   Polymerization degree about 2,000; Saponification degree 88%

Matting agent(1)

-   -   Latex of sphere polymethyl methacrylate (average particle        diameter: 3 μm)

Hardener (1)

-   -   CH₂═CHSO₂CH₂CONH(CH₂)₂NHCOCH₂SO₂CH═CH₂

Hardener (2)

-   -   CH₂═CHSO₂CH₂CONH(CH₂)₃NHCOCH₂SO₂CH═CH₂        Formation of a Cover Sheet

Application was performed onto a transparent support having a thicknessof 75 μm so as to have a layer structure shown in Table 37. Thus, acover sheet was formed.

TABLE 37 Layer constitution of cover sheet Coated Number of amount layerName of layer Additive (g/m²) Third Temperature Temperature compensating0.43 layer compensating polymer (1) layer Temperature compensating 1.20polymer (2) Surfactant (8) 0.0024 Second Alkali barrier Acetylcellulose2.87 layer layer (Acetylation degree 51%) Additive (19) 0.20 Additive(20) 0.20 Hardener (2) 0.35 First Neutralization Acid polymer (1) 10.40layer layer Acetylcellulose 0.70 (Acetylation degree 45%) Hardener (5)0.049 Support(75 μm of polyethylene terephthalate undercoated by gelatinand containing additive (21) for preventing light piping) Backing CurlAcetylcellulose 9.10 layer controlling (Acetylation degree 55%) layerSilica (average particle diameter: 0.04 3˜4 μm)

The following will show chemical structures of compounds to be used inthe cover sheet.

The following will describe the formulation of an alkaline processingcomposition to be used.

Silver nitrate  0.10 g Carbon black (Dai-nichi Seika Co.)   160 gAdditive (27)  8.60 g Na salt of carboxymethyl cellulose  58.0 gBenzylalcohol  2.50 g Additive (28)  2.10 g Potassium sulfite(anhydride)  1.90 g 5-methylbenzotriazole  2.50 g1-p-tolyl-4-hydroxymethyl-4-methyl-  7.00 g 3-pyrazolidone1-phenyl-4-hydroxymethyl-4-methyl-  10.0 g 3-pyrazolidone Potassiumhydroxide  56.0 g Aluminum nitrate  0.60 g Zinc nitrate  0.60 g Additive(29)  6.60 g Additive (14)  1.80 g 1,2-benzisothiazoline-3-one 0.003 g

Preparation of Light-Sensitive Materials 302-304

Light-sensitive materials 302-304 were prepared in the same manner as inthe preparation of the light-sensitive material 301, except that thecolor-developing agents and the couplers in the 13th layer and the 19thlayer of the light-sensitive material 301 were replaced by equivalentmoles of the following color-developing agents and couplers shown inTable 38.

TABLE 38 Color Color developing developing agent of Coupler of agent of19th Coupler of Sample No. 13th layer 13th layer layer 19th layerRemarks 301 Color Magenta Color Yellow Comparative developing coupler{circle around (1)} developing coupler {circle around (1)} example agent{circle around (1)} agent {circle around (1)} 302 R40 Cp-13 R40 Cp-11This invention 303 R41 Cp-14 R22 Cp-11 This invention 304 R42 Cp-13 R40Cp-12 This invention

Then, each of the light-sensitive elements 301-304 was subjected to grayexposure from the side of the emulsion layer through a continuous wedge.Subsequently the cover sheet was put on the exposed element and then apressing roller was used to develop the alkaline processing compositionbetween the sheet and the element to have a thickness of 55 μm. Theprocessing was performed at 25° C. After two hours, the highest transferdensities of yellow and magenta were measured with a color densitometer.Furthermore, after irradiation with a fluorescent lamp having anilluminance of 17,000 lux for 2 weeks, the highest transfer densities ofyellow and magenta were also measured.

Measured results are shown in Table 39.

TABLE 39 Maximum transferred density Maximum transferred after 2 weeksirradiation with density after 2 hours fluorescent lamp Sample No.Yellow Magenta Yellow Magenta Remarks 301 1.57 1.82 0.56 0.54Comparative example 302 1.80 2.05 1.65 1.83 This invention 303 1.92 2.251.85 1.99 This invention 304 1.89 2.23 1.74 1.94 This invention

As is apparent from comparison with the sample 301 (Comparative example)with the samples 302, 303 and 304 (This invention), the compounds of thepresent invention were superior in color-forming property and imagestability than known compounds.

Example 2-1

A dye fixation material (image-receiving element) R101 was formed in thesame manner as in the above Example 1-1, except that in Example 2-1, thefollowing was used as the anionic surfactant (2).

Then, a light-sensitive material for heat-development was produced bythe following method.

The light-sensitive silver halide emulsions, and the colloidal silveremulsion dispersion were made in the same manner as in the above Example1-1, except that in the preparation of the Light-sensitive silver halideemulsion (3), the sensitizing dye {circle around (3)} (that was added inthe Example 1-1 at the time-of chemical sensitization) was not added.

Then, the preparation methods of gelatin dispersions of hydrophobicadditives are described.

Gelatin dispersions of a yellow-dye-providing compound, amagenta-dye-providing compound, and a cyan-dye-providing compound, whoseformulations are shown in Table 40, were prepared, respectively. Thatis, the oil phase components were dissolved by heating to about 70° C.,to form a uniform solution, and to the resultant solution, were addedthe aqueous phase components that had been heated to about 60° C.,followed by stirring to mix and dispersing by a homogenizer for 10 minat 10,000 rpm. To the resultant dispersion, was added additional water,followed by stirring, to obtain a uniform dispersion.

Furthermore, the gelatin dispersion of the cyan dye-providing compoundwas subjected to ultrafiltration using an ultrafiltration module(ultrafiltration module: ACV-3050, trade name, made by Asashi ChemicalCo., Ltd.), so that the amount thereof would be 1/17.6 of the amount ofethyl acetate shown in Table 40.

TABLE 40 Composition of dispersion Yellow Magenta Cyan OilYellow-dye-providing compound {circle around (1)}  1.68 g None Nonephase Yellow-dye-providing compound {circle around (2)}  4.03 g NoneNone Cyan-dye-providing compound {circle around (1)} None None 4.45 gMagenta-dye-providing compound {circle around (1)} None  5.27 g NoneReducing agent {circle around (1)}  0.47 g  0.06 g 0.29 g Antifoggant{circle around (3)}  0.1 g None 0.06 g Antifoggant {circle around (4)}None 0.021 g None Surfactant {circle around (1)}  0.6 g  0.23 g 0.45 gHigh-boiling solvent {circle around (1)}  0.84 g None 1.34 gHigh-boiling solvent {circle around (2)}  2.01 g  2.63 g 4.47 gDevelopment accelerator {circle around (1)}  1.01 g None None Dye (a) 0.59 g None 0.14 g Water 0.19 ml None  0.3 g Ethyl acetate   10 ml 16ml  16 ml Aqueous phase Lime-processed gelatin  5.5 g  3.1 g  2.4 gCalcium nitrate  0.05 g  0.04 g None Surfactant {circle around (1)} NoneNone None Sodium hydroxide aq. soln. (1 mol/l) None None 0.07 gCarboxymethyl cellulose None None   31 g Water   35 ml 31 ml   40 mlWater (after emulsification)   40 ml 43 ml 0.03 ml Antiseptic {circlearound (1)} 0.003 g 0.002 g None

A gelatin dispersion of Antifoggant {circle around (4)} whoseformulation is shown in Table 41 was prepared. That is, the oil phasecomponents were dissolved by heating to about 60° C. to form a solution,and to the resultant solution, were added the aqueous phase componentsthat had been heated to about 60° C., and after stirring and mixingthem, the resultant mixture was dispersed for 10 min at 10,000 rpm by ahomogenizer, to obtain a uniform dispersion.

TABLE 42 Composition of dispersion Oil phase Antifoggant {circle around(4)} 0.8 g Reducing agent {circle around (1)} 0.1 g High-boiling solvent{circle around (2)} 2.3 g High-boiling solvent {circle around (5)} 0.2 gSurfactant {circle around (1)} 0.5 g Surfactant {circle around (4)} 0.5g Ethyl acetate 10.0 ml Aqueous phase Acid-processed gelatin 10.0 gAntiseptic {circle around (1)} 0.004 g Calcium nitrate 0.1 g Water 35.0ml Additional Water 46 ml

A gelatin dispersion of Reducing Agent {circle around (2)} whoseformulation is shown in Table 42 was prepared. That is, the oil phasecomponents were dissolved by heating to about 60° C. to form a solution,and to the resultant solution, were added the aqueous phase componentsthat had been heated to about 60° C., and after stirring and mixingthem, the resultant mixture was dispersed for 10 min at 10,000 rpm by ahomogenizer, to obtain a uniform dispersion. From the thus-obtaineddispersion, ethyl acetate was removed off using a vacuum organic solventremoving apparatus.

TABLE 43 Composition of dispersion Oil Reducing agent {circle around(2)} 7.5 g phase High-boiling solvent {circle around (1)} 4.7 gSurfactant {circle around (1)} 1.9 g Ethyl acetate 14.4 ml AqueousAcid-processed gelatin 10.0 g phase Antiseptic {circle around (1)} 0.002g Antiseptic {circle around (4)} 1.004 g Calcium nitrate 2.1 g Water136.7 ml

A dispersion of Polymer Latex (a) whose formulation is shown in Table 43was prepared. That is, while a mixed solution of Polymer Latex (a),Surfactant {circle around (5)}, and water whose amounts are shown inTable 43 was stirred, Anionic Surfactant {circle around (6)} was addedthereto, over 10 min, to obtain a uniform dispersion. The resultingdispersion was repeatedly diluted with water and concentrated using aultrafiltration module (Ultrafiltration Module: ACV-3050, trade name,manufactured by Asahi Chemical Industry Co., Ltd.), to bring the saltconcentration of the dispersion to 1/9, thereby obtaining a dispersion.

TABLE 43 Composition of dispersion Polymer Latex (a) aqueous solution(solid content 13%)  108 ml Surfactant {circle around (5)}  20 g  Anionic surfactant {circle around (6)} aqueous solution (5%)  600 mlWater 1232 ml

A gelatin dispersion of Stabilizer {circle around (1)} whose formulationis shown in Table 44 was prepared. That is, the oil phase componentswere dissolved at room temperature to form a solution, and to theresultant solution, were added the aqueous phase components that hadbeen heated to about 40° C., and after stirring and mixing them, theresultant mixture was dispersed for 10 min at 10,000 rpm by ahomogenizer. To the resultant dispersion, was added additional water,followed by stirring, thereby obtaining a uniform dispersion.

TABLE 44 Composition of dispersion Oil phase Stabilizer {circle around(1)}  4.0 g Sodium hydroxide  0.3 g Methanol 62.8 g High-boiling solvent 0.9 g Aqueous Gelatin from which calcium had been   10 g phase removed(Ca content 100 ppm or less) Antiseptic{circle around (1)} 0.04 g Water320.5 ml

A gelatin dispersion of zinc hydroxide was prepared according to theformulation shown in Table 45. That is, after the components were mixedand dissolved, dispersing was carried out for 30 min in a mill, usingglass beads having an average particle diameter of 0.75 mm. Then theglass beads were separated and removed off, to obtain a uniformdispersion. (Zinc hydroxide having a grain size of 0.25 μm was used.)

TABLE 45 Composition of dispersion Zinc hydroxide 15.9 g Carboxymethylcellulose  0.7 g Poly(sodium acrylate) 1.07 g Lime-processed gelatin 4.2 g Water    100 ml High-boiling solvent {circle around (2)}  0.4 g

The preparation method of a gelatin dispersion of a matt agent that wasto be added to the protective layer is described.

A solution containing PMMA dissolved in methylene chloride was added,together with a small amount of a surfactant, to gelatin, and they werestirred and dispersed at high speed. Then the methylene chloride wasremoved off using a vacuum solvent removing apparatus, to obtain auniform dispersion having an average particle size of 4.3 μm.

High-boiling organic solvent {circle around (1)}

-   -   (C₄H₉(C₂H₅)CHCH₂O)₃—P═O

Hardener {circle around (1)}

-   -   CH₂═CHSO₂CH₂SO₂CH═CH₂

High-boiling organic solvent {circle around (5)}

-   -   C₂₆H_(46.9)Cl_(7.1)    -   EMPARA 40 (trade name: manufactured by Ajinomoto K. K.)

Using the above materials, Light-Sensitive Material 1101 shown in Tables46 and 47 was prepared.

TABLE 46 Constitution of Main Materials of Light-Sensitive Material 1101Number Added of Name of amount layer layer Additive (mg/m²) SeventhProtective Acid-processed gelatin 378 layer layer Reducing agent {circlearound (2)} 70 High-boiling solvent {circle around (1)} 44 Colloidalsilver grains 2 Matting agent (PMMA resin) 17 Surfactant {circle around(1)} 19 Surfactant {circle around (2)} 16 Surfactant {circle around (3)}2 Surfactant {circle around (4)} 12 Surfactant {circle around (6)} 17Dispersion of Polymer Latex a 14 Calcium nitrate 5 Sixth IntermediateLime-processed gelatin 882 layer layer Zinic hydroxide 577 Antifoggant{circle around (4)} 18 Reducing agent {circle around (1)} 2 High-boilingsolvent {circle around (2)} 54 High-boiling solvent {circle around (5)}6 Surfactant {circle around (1)} 1 Surfactant {circle around (2)} 0.5Surfactant {circle around (7)} 11 Water-soluble polymer {circle around(1)} 5 Calcium nitrate 17 Fifth 680 nm- Lime-processed gelatin 428 layerlight- Light-sensitive silver halide emulsion(1) 287 sensitiveMagenta-dye-providing compound {circle around (1)} 487 layerHigh-boiling solvent {circle around (2)} 244 Reducing agent {circlearound (1)} 18 Antifoggant {circle around (4)} 20 Surfactant {circlearound (1)} 22 Water-soluble polymer {circle around (1)} 11 ForthIntermediate Lime-processed gelatin 416 layer layer Zinic hidroxide 271Antifoggant {circle around (4)} 8 Reducing agent {circle around (1)} 1High-boiling solvent {circle around (2)} 25 High-boiling solvent {circlearound (5)} 378 Surfactant {circle around (1)} 5 Surfactant {circlearound (2)} 0.3 Surfactant {circle around (7)} 5 Water-soluble polymer{circle around (1)} 2 Calcium nitrate 8

TABLE 47 Number Added of Name of amount layer layer Additive (mg/m²)Third 750 nm- Lime-processed gelatin 404 layer light- Light-sensitivesilver halide 184 sensitive emulsion (2) layer Stabilizer {circle around(1)} 8 Cyan-dye-providing compound {circle around (1)} 428 Dye (a) 13High-boiling solvent {circle around (1)} 128 High-boiling solvent{circle around (2)} 429 Reducing agent {circle around (1)} 56Antifoggant {circle around (3)} 5 Surfactant {circle around (1)} 43Carboxymethyl cellulose 7 Water-soluble polymer {circle around (1)} 9Second Intermediate Lime-processed gelatin 708 layer layer Antifoggant{circle around (5)} 4 Reducing agent {circle around (1)} 2 Surfactant{circle around (2)} 104 Surfactant {circle around (5)} 14 Calciumnitrate 5 First 810 nm- Lime-processed gelatin 569 layer light-Light-sensitive silver halide 330 sensitive emulsion (3) layerFine-grain silver chloride emulsion 30 Stabilizer {circle around (1)} 8Yellow-dye-providing compound {circle around (1)} 119Yellow-dye-providing compound {circle around (2)} 285 Sensitizing dye{circle around (3)} 0.1 Dye (a) 42 High-boiling solvent {circle around(1)} 59 High-boiling solvent {circle around (2)} 143 Surfactant {circlearound (1)} 41 Reducing agent {circle around (1)} 66 Developmentaccelerator {circle around (1)} 71 Antifoggant {circle around (3)} 6Water-soluble polymer {circle around (2)} 41 Hardener {circle around(1)} 45 Support (Paper support whose both surfaces were laminated withpolyethylene: thickness 135 μm)

Light-sensitive materials 1102 and 1103 were formed in the same manneras the light-sensitive material 1101, except that the gelatin dispersionof the magenta dye-providing compound of the fifth layer-in thelight-sensitive material 1101 was changed to each gelatin dispersion ofdye-providing compound shown in the following Table 48.

Light-sensitive materials 1104 and 1105 were formed in the same manneras the light-sensitive material 1101, except that the gelatin dispersionof the yellow dye-providing compounds of the first layer in thelight-sensitive material 1101 was changed to each gelatin dispersion ofdye-providing compound shown in the following Table 48.

TABLE 48 Light- Magenta-dye- sensitive Yellow-dye-providing providingmaterial compound compound Remarks 1101 Yellow-dye-providingMagenta-dye- Comparative compound {circle around (1)} providing exampleYellow-dye-providing compound {circle around (1)} compound {circlearound (2)} 1102 — K-1 This invention 1103 — K-4 This invention 1104K-7  — This invention 1105 K-10 — This invention Notes) “—” indicatesthat no change from the sample 1101 was performed.

Each of the light-sensitive materials 1101 to 1105 was combined with thedye fixation material R101, and then the combination was subjected toexposure to light and development, using PICTROGRAPHY 3000 (trade name)made by Fuji Photo Film Co., Ltd., to obtain an image on theimage-receiving material.

A densitometer X rite 404, (trade name) made by X rite company, was usedto measure the reflection density of the image. The maximum density(Dmax) and the minimum density (Dmin) of each of magenta and yellow weremeasured and evaluated.

The images obtained from the light-sensitive materials were irradiatedwith Xenon light having an illumination of 170,000 lux for a week. Onthe portions having-a magnet density or a yellow density of 1.0, dyeremaining rates were obtained. The results are shown in Table 49.

TABLE 49 Light- sensi- Residual tive rate of material Dmax Dmin dye (%)Hue Remarks 1101 2.12 0.16 88.7 Magenta Comparative example 1102 2.420.14 88.2 Magenta This invention 1103 2.25 0.14 86.7 Magenta Thisinvention 1101 1.96 0.14 90.7 Yellow Comparative example 1104 2.2 0.1290 Yellow This invention 1105 2.14 0.1 92.4 Yellow This invention

The results in Table 49 demonstrate that the compound of the presentinvention had both of high developed color density and excellentfastness to light.

Example 2-2

Each of the compound examples (K-2), (K-5), (K-8) and (K-11) was usedand evaluated in the same manner as in Examples described inJP-A-8-137072. As a result, it was found that the compound of thepresent invention had both the high developed color density and the highfastness to light.

Example 2-3

Each of the compound examples (K-3), (K-6), (K-9) and (K-12) was usedand evaluated in the same manner as in Examples described inJP-A-6-332131. As a result, it was found that the compound of thepresent invention had a sharpness-improving effect and further had highdeveloped color density and high fastness to light.

Example 2-4

The absorbances of the exemplified dye (DYE-7) and the dye forcomparison (D-1) in N,N-dimethylformamide were measured. The resultsthereof are shown in FIG. 1. FIG. 1 demonstrates that the dye of thepresent invention exhibited a good absorbance property.

Having described our invention as related to the present embodiments, itis our intention that the invention not be limited by any of the detailsof the description, unless otherwise specified, but rather be construedbroadly within its spirit and scope as set out in the accompanyingclaims.

1. An azo dye represented by the following formula (2-1):

wherein R¹ represents a hydrogen atom or a substituent, and A is a groupto give a coupler which has been used in a silver halide photographiclight sensitive material.
 2. An azo dye represented by the followingformula (2-1):

wherein R¹ represents a hydrogen atom or a substituent, and A in theformula (2-1) is a group represented by the following formula (2-2):

wherein R², R³, R⁴ and R⁵ each represents a hydrogen atom or asubstituent, and R² and R³ and/or R⁴ and R⁵ may bond together to form aring, and * represents a position which is bonded to the azo moiety inthe formula (2-1).
 3. An azo dye represented by the following formula(2-1):

wherein R¹ represents a hydrogen atom or a substituent, and A in theformula (2-1) is a group represented by the following formula (2-3):

wherein Cα represents a carbon atom, EWG represents a cyano, carbamoylor alkoxycarbonyl group, M represents a group of atoms necessary to formtogether with the Cα a 5- or 6-membered aromatic heteroring, and *represents a position which is bonded to the azo moiety in the formula(2-1).
 4. An azo dye represented by the following formula (2-1):

wherein R¹ represents a hydrogen atom or a substituent, and A in theformula (2-1) is a group represented by the following formula (2-4):

wherein R⁶ represents a hydrogen atom or a substituent, Cβ represents agroup of atoms necessary to form together with the N—C—NH a 5- or6-membered aromatic heteroring, and * represents a position which isbonded to the azo moiety in the formula (2-1).
 5. The azo dye of claim1, wherein R¹ represents a hydrogen atom, or a substituent selected fromthe group consisting of halogen atoms, alkyl, alkenyl, alkynyl, aryl,heterocyclic, cyano, hydroxyl, nitro, carboxyl, alkoxy, aryloxy,silyloxy, heterocylic oxy, acyloxy, carbamoyloxy, alkoxycarbonyloxy,aryloxycarbonyloxy, amino, acylamino, aminocarbonylamino,alkoxycarbonylamino, aryloxycarbonylamino, sulfamoylamino, alkyl- andaryl-sulfonylamino, mercapto, alkylthio, arylthio, heterocyclic thio,sulfamoyl, sulfo, alky- and aryl-sulfinyl, alkyl- and aryl-sulfonyl,acyl, aryloxycarbonyl, alkoxycarbonyl, carbamoyl, arylazo, heterocyclicazo, imido, phosphino, phosphinyl, phosphinyloxy, phosphinylamino, andsilyl groups.
 6. The azo dye of claim 1, wherein the substituentrepresented by R¹ is selected from the group consisting of fluorine,chlorine, bromine, iodine, straight-chain, branched or cyclic, andsubstituted or unsubstituted alkyl groups, and substituted orunsubstituted cycloalkyl groups having 3-12 carbon atoms.
 7. The azo dyeof claim 1, wherein the substituent represented by R¹ is selected fromthe group consisting of halogen atoms, alkyl, aryl and heterocyclicgroups.
 8. The azo dye of claim 2, wherein R¹ represents a hydrogenatom, or a substituent selected from the group consisting of halogenatoms, alkyl, alkenyl, alkynyl, aryl, heterocyclic, cyano, hydroxyl,nitro, carboxyl, alkoxy, aryloxy, silyloxy, heterocyclic oxy, acyloxy,carbamoyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, amino, acylamino,aminocarbonylamino, alkoxycarbonylamino, aryloxcarbonylamino,sulfamoylamino, alkyl- and aryl-sulfonylamino, mercapto, alkylthio,arylthio, heterocyclic thio, sulfamoyl, sulfo, alky- and aryl-sulfinyl,alkyl- and aryl-sulfonyl, acyl, aryloxycarbonyl, alkoxycarbonyl,carbamoyl, arylazo, heterocyclic azo, imido, phosphino, phosphinyl,phosphinyloxy, phosphinylamino, and silyo groups.
 9. The azo dye ofclaim 2, wherein the substituent represented by each of R¹, R², R³, R⁴and R⁵ is independently selected from the group consisting of halogenatoms, alkyl, cyano, alkoxy, acylamino, aminocarbonylamino,alkoxycarbonylamino, alkyl- and aryl-sulfonylamino, sulfamoyl, sulfo,alkyl- and aryl-sulfinyl, alkyl- and aryl-sulfonyl, acyl,alkoxycarbonyl, and carbamoyl group.
 10. The azo dye of claim 3, whereinR¹ represents a hydrogen atom or a substituent selected from the groupconsisting of halogen atoms, alkyl, alkenyl, alkynyl, aryl,heterocyclic, cyano, hydroxyl, nitro, carboxyl, alkoxy, aryloxy,silyloxy, heterocyclic oxy, acyloxy, carbamoyloxy, alkoxcarbonyloxy,aryloxcarbonyloxy, amino, acylamino, aminocarbonylamino,alkoxycarbonylamino, aryloxcarbonylamino, sulfamoylamino, alkyl- andaryl-sulfonylamino, mercapto, alkylthio, arylthio, heterocyclic thio,sulfamoyl, sulfo, alky- and aryl-sulfinyl, alkyl- and aryl-sulfonyl,acyl, aryloxcarbonyl, alkoxycarbonyl, carbamoyl, arylazo, heterocyclicazo, imido, phosphino, phosphinyl, phosphinyloxy, phosphinylamino, andsilyl groups.
 11. The azo dye of claim 3, wherein the aromaticheteroring is selected from the group consisting of pyrrole, imidazole,pyrazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, 1,3,4-thiadiazole,1,2,4-thiadiazole, 1,3,4-oxadiazole, 1,2,4-oxadiazole, thiazole,oxazole, isothiazole, isooxazole, thiophene, benzoxazole, benzimidazole,benzothiazole, benziosothiazole, pyrazine, pyrimidine, pyridazine,1,2,4-triazine, 1,3,5-triazine, quinazoline, quinazolone, quinoxaline,synoline, pteridine, and thiazinone rings.
 12. The azo dye of claim 3,wherein the aromatic heteroring is selected from the group consisting of1,3,4-thiadiazole, 1,2,4-thiadiazole, thiazole, benzothiazole,benzoisothiazole and pyrimidine rings.
 13. The azo dye of claim 4,wherein R¹ and R⁶ independently represents a hydrogen atom, or asubstituent selected from the group consisting of halogen atoms, alkyl,alkenyl, alkynyl, aryl, heterocyclic, cyano, hydroxyl, nitro, carboxyl,alkoxy, aryloxy, silyloxy, heterocylic oxy, acyloxy, carbamoyloxy,alkoxycarbonyloxy, aryloxycarbonyloxy, amino, acylamino,aminocarbonylamino, alkoxycarbonylamino, aryloxcarbonylamino,sulfamoylamino, alkyl- and aryl-sulfonylamino, mercapto, alkylthio,arylthio, heterocyclic thio, sulfamoyl, sulfo, alky- and aryl-sulfinyl,alkyl- and aryl-sulfonyl, acyl, aryloxycarbonyl, alkoxycarbonyl,carbamoyl, arylazo, heterocyclic azo, imido, phosphino, phosphinyl,phosphinyloxy, phosphiylamino, and silyl groups.
 14. The azo dye ofclaim 4, wherein the substituent represented by each of R¹ and R⁶ isindependently selected from the group consisting of alkyl, alkoxy,phenoxy, acylamino, alkoxycarbonyl and carbamoyl groups.